Chromium compounds and uses thereof

ABSTRACT

Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support to trimerize and/or polymerize olefins.

This application is a divisional application of Ser. No. 07/698,515,filed May 10, 1991 now U.S. Pat. No. 5,198,563, which is a division ofSer. No. 07/454,554, filed Dec. 21, 1989, abandoned, which is acontinuation-in-part of application Ser. No. 07/392,688, filed Aug. 10,1989, abandoned.

BACKGROUND OF THE INVENTION

This invention relates to chromium catalysts to trimerize and/orpolymerize olefins. This invention also relates to a process totrimerize and/or polymerize olefins.

Supported chromium oxide catalysts have been a dominant factor in theproduction of olefin polymers, such as polyethylene of copolymers ofethylene and hexene. These catalysts can be used in a variety ofpolymerization processes. However, most known chromium compounds must besupported to be catalytically active. Furthermore, most supportedchromium compounds are useful only for olefin polymerization. If anolefin copolymer is desired, the polymerization process becomes morecomplex in that two different monomers must be fed to the polymerizationreactor.

Olefin trimerization catalysts are also known in the art, but usuallylack selectivity to a desired product and also have a low product yield.However, olefin trimerization, if done efficiently, is a process toprovide useful olefins, which in turn, can be further trimerized or,optionally, incorporated into a polymeriation process.

SUMMARY OF THE INVENTION

Therefore, it is an object of this invention to provide novel chromiumcompounds.

It is yet another object of this invention to provide a process toprepare at least one novel chromium compound.

It is a further object of this invention to provide an improved processto trimerize olefins.

It is yet another object of this invention to provide a process topolymerize olefins.

It is a further object of this invention to provide an improved olefintrimerization catalyst.

It is yet another object of this invention to provide an olefinpolymerization catalyst.

Therefore, in accordance with this invention, novel chromium-containingcompounds are prepared from a reaction mixture comprising a chromiumsalt, a metal amide, and any electron pair donor solvent, such as, forexample, an ether.

In accordance with another embodiment of this invention thischromium-containing compound can be used, either supported orunsupported, to trimerize or polymerize olefins.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a computer generated ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a simplified structural representation or formula, of amolecule of Product I, Cr₅ (NC₄ H₄)₁₀ (OC₄ H₈)₄, as determined by singlecrystal x-ray crystallography, and

FIG. 2 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 1.

FIG. 3 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct III, [Cr(NC₄ H₄)₄ ]⁻², as determined by single crystal x-raycrystallography.

FIG. 4 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 3, however, the entire crystal structure or lattice, with theformula Cr(NC₄ H₄)₄ Na₂.20C₄ H₈ is shown.

FIG. 5 is a computer generated ORTEP drawing of the structure, or asimplified structural representation or formula, of a molecule ofProduct IV, [Cr(NC₄ H₄)₅ (OC₄ H₈)]⁻², as determined by single crystalx-ray crystallography, and

FIG. 6 is a further simplified ball and stick projection, with theexception of the chromium atoms which are represented as thermalellipsoids, or a structural representation, of the same molecule shownin FIG. 5, however the entire crystal structure or lattice, with theformula [Cr(NC₄ H₄)₅ (OC₄ H₈)][Na]₂.4(OC₄ H₈), is shown.

FIG. 7 is a computer generated ORTEP drawing of a molecule of Product V,Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na, which includes the entire crystalstructure or lattice, as determined by single crystal x-raycrystallography.

FIG. 8 is a further simplified ball and stick projection of samemolecule shown in FIG. 7.

FIG. 9 is a further simplified ball and stick projection of [Cr(NC₄ H₄)₃Cl(O₂ C₂ H₄ (CH₃)₂)]⁻¹, with the exception of the chromium atom which isrepresented as a thermal ellipsoid. This is the same molecule as thatshown in FIGS. 7 and 8, however, the entire crystal structure, orlattice, is not shown in FIG. 9.

DETAILED DESCRIPTION OF THE INVENTION The Chromium Compounds

The inventive chromium compounds, which can be used preferably forolefin trimerization and, optionally, olefin polymerization, can beproduced by forming a reaction mixture comprising a chromium salt, ametal amide, and any electron pair donor solvent, such as, for example,an ether. As used in this disclosure, the inventive chromium compoundsare referred to by a variety of interchangeable names, such as inventiveor novel chromium compound(s), chromium complex(es), chromium pyrrolecomplex(es) and/or chromium pyrrolide.

The chromium salt can be one or more organic or inorganic chromiumsalts, wherein the chromium oxidation state is from 0 to 6. As used inthis disclosure, chromium metal is included in this definition of achromium salt. Generally, the chromium salt will have a formula ofCrX_(n), wherein X can be the same or different and can be any organicor inorganic radical, and n is an integer from 1 to 6. Exemplary organicradicals can have from about 1 to about 20 carbon atoms, and areselected from the group consisting of alkoxy, ester, ketone, and/oramido radicals. The organic radicals can be straight-chained orbranched, cyclic or acyclic, aromatic or aliphatic, and can be made ofmixed aliphatic, aromatic, and/or cycloaliphatic groups. Exemplaryinorganic radicals include, but are not limited to halides, sulfates,and/or oxides.

Preferably, the chromium salt is a halide, such as, for example chromousbromide, chromic bromide, chromous iodide, chromic iodide, chromousfluoride, chromic fluoride, chromous chloride, chromic chloride, andmixtures thereof. Most preferably, the chromium salt is a chloride, suchas, for example chromous chloride and/or chromic chloride, due to simpleseparation of the reaction by-products such as, for example, sodiumchloride, as well as relatively low cost.

The metal amide can be any metal amide that will react with a chromiumsalt to form a chromium-amido complex. Broadly, the metal amide can beany heteroleptic or homoleptic metal complex or salt, wherein the amideradical can be any nitrogen-containing organic radical. The metal amidecan be either affirmatively added to the reaction, or generated in-situ.Generally, the metal amide will have from about 1 to about 20 carbonatoms. Exemplary metal amides include, but are not limited to, primaryand/or secondary amines, any alkali metal (Group IA, and includinghydrogen, of the Periodic Table) amide and/or any alkaline earth metal(Group IIA of the Periodic Table) amide. The hydrocarbyl portion of thesalt of the metal amide is selected from the group consisting ofstraight chain or branched, cyclic or acyclic, aromatic or aliphatic,and mixtures of two or more thereof. Preferably, the metal amide isselected from a Group IA, and including hydrogen, or Group IIA metalamide, due to ease of reaction with chromium halides.

Exemplary preferred metal amides include, but are not limited to,lithium dimethylamide, lithium diethylamide, lithium diisopropylamide,lithium dicyclohexylamide, sodium bis(trimethylsilyl)amide, sodiumindolide, sodium pyrrolide, and mixtures of two or more thereof. Mostpreferably, the metal amide is a pyrrolide. As used in this disclosure,a pyrrolide is defined as a compound comprising a 5-membered,nitrogen-containing heterocycle, such as, for example, pyrrole,derivatives of pyrrole, and mixtures thereof. Exemplary pyrrolides areselected from the group consisting of hydrogen pyrrolide (pyrrole),lithium pyrrolide, sodium pyrrolide, potassium pyrrolide, cesiumpyrrolide, and/or the salts of substituted pyrrolides, because of highreactivity and activity with the other reactants. Examples of salts ofsubstituted pyrrolides include, but are not limited to sodium2,5-dimethyl pyrrolide and/or 3,4-dimethyl pyrrolide. When the metalamide is a pyrrolide ligand, the resultant chromium compound is achromium pyrrolide.

The electron pair donor solvent can be any electron pair donor solventto affect a reaction between the chromium salt and the metal amide.While not wishing to be bound by theory, it is believed that theelectron pair donor solvent can be a reaction solvent, as well as apossible reactant. Exemplary electron pair donor solvents include, butare not limited to, nitrogen-,oxygen-, phosphorous-, and/orsulfur-containing compounds and/or ethers.

Exemplary nitrogen-containing compounds include, but are not limited tonitriles, such as, for example, acetonitrile; amines, such as, forexample, pyridine, and/or amides. Additional exemplarynitrogen-containing compounds include, but are not limited to,nitromethane, dimethylpyridine, dimethylformamide, N-methylformamide,aniline, nitrobenzene, tetramethyldiaminomethane, hexamethyldisilazane,and/or pyrrolidone.

Exemplary oxygen-containing compounds include, but are not limited to,acetone, ethyl acetate, methyl acetate, methanol, ethanol, ethyl methylketone, acetaldehyde, furan, and/or hexamethyldisiloxane.

Exemplary phosphorous-containing compounds include, but are not limitedto, hexamethylphosphoramide, hexamethylphosphorous triamide,triethylphosphite, tributylphosphine oxide, and/or triethylphosphine.

Exemplary sulfur-containing compounds include, but are not limited to,carbon disulfide, dimethylsulfoxide, tetramethylene sulfone, triophene,and/or dimethylsulfide or mixtures thereof.

The ether in the reaction mixture can be one or more ether compounds toaffect a reaction between the chromium salt and the metal amide. Whilenot wishing to be bound by theory, it is believed that the ether can bea reaction solvent, as well as a possible reactant. The ether can be anyaliphatic and/or aromatic compound containing an R-O-R functionality,wherein the R groups can be the same or different, but preferably is nothydrogen. Preferred ethers are aliphatic ethers, for safety reasons inthat aromatic ethers are human toxins. Furthermore, the preferred ethersare those which facilitate a reaction between a chromium halide and aGroup IA or Group IIA metal pyrrolide, and also can be easily removedfrom the reaction mixture. Exemplary compounds include, but are notlimited to, tetrahydrofuran, dioxane, diethylether, dimethoxyethane(glyme), diglyme, triglyme, and mixtures of two or more dimethoxyethane(glyme), diglyme, triglyme, and mixtures of two or more thereof. Mostpreferably, the ether is selected from the group consisting oftetrahydrofuran, derivatives of tetrahydrofuran, dimethoxyethane,derivatives of dimethoxyethane, and mixtures thereof, for the reasonsgiven above, as well as the reason that the preferred salt of an amineis soluble in these ethers.

The amount of each reactant used to prepare one or more of the novelchromium compounds can vary, based on the desired chromium compoundproduct. Any amount of each reactant can be used to produce the novelchromium compounds, depending on the desired product. Different reactionstoichiometries can produce different chromium compounds. For example,the reaction of about one mole of chromium (II) with about two moles ofsodium pyrrolide can produce different products than reacting about onemole of chromium (II) with an excess of sodium pyrrolide. Furthermore,as stated earlier, selection of different, although similar reactants,can produce different products. For example, using eithertetrahydrofuran or dimethoxyethane can result in a different reactionproduct.

The three reactants can be combined in any manner under conditionssuitable to form a solution comprising one or more of the inventivechromium compounds. The reaction preferably occurs in the absence ofoxygen and therefore under an inert, such as, for example, nitrogenand/or argon. The reaction pressure can be any pressure sufficient tomaintain the reactants in a liquid state. Generally, pressure within therange of from about atmospheric pressure to about three atmospheres areacceptable. For ease of operation atmospheric pressure is generallyemployed.

The reaction temperature can be any temperature which maintains theether in a liquid form. In order to effectuate a more efficientreaction, temperatures near the boiling point of the ether arepreferred. Most preferably, the reaction temperature is at the boilingpoint of the ether and the reaction mixture is refluxed for a period oftime.

The reaction time can be any amount of time necessary for the reactionto occur. Depending on the reactants, as well as the reactiontemperature and pressure, reaction time can vary from about 1 minute toabout 1 week. Usually, reaction time ranges from about 3 hours to about5 days. Under optimum conditions, the reaction time can be within therange of from about 3 to about 48 hours.

After the reaction is complete, a solid reaction product can berecovered by any method known in the art. Preferably, though notrequired, upon completion of the reaction, the reaction mixture first isfiltered to remove any reaction insoluble by-products such as, forexample, salts, like sodium chloride, prior to any other treatment.Although removal of any reaction by-products is not necessary, suchremoval preferably is done in order to expedite later purification ofthe chromium product. After filtering, one exemplary method to recover asolid reaction product is to remove the excess ether from the reactionmixture. The excess electron pair donor solvent, such as, for example anether, can be removed according to any method known in the art.Exemplary electron pair donor solvent, such as, for example an ether,removal methods include, but are not limited to, slow evaporation, undervacuum and/or a nitrogen purge.

Other electron pair donor solvent, such as, for example an ether,removal procedures can be used either alone or in combination. Forexample, the reaction mixture can be filtered and then vacuum dried.Preferably, the reaction mixture is heated slowly and maintained attemperature within the range of about 10° C. to about 300° C.,preferably about 25° C. to about 200° C., under a vacuum, for safety, toremove the excess electron pair donor solvent, such as, for example anether. The resultant solid reaction product is one or more of theinventive chromium compounds.

Alternatively, the reaction mixture can be filtered to remove any solidreaction by-product solids and the filtered reaction mixture can becontacted with a non-polar organic solvent. Addition of a non-polarorganic solvent causes one or more of the inventive chromium compoundsto form a solid precipitate. Exemplary non-polar organic solventinclude, but are not limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably pentane is added to the filteredreaction mixture because of the availability and ease of use.

The precipitated inventive chromium compounds can be recovered by anymethod known in the art. The simplest procedure to recover the inventiveprecipitated chromium compounds is by filtration.

The reaction mixture and the resultant solid reaction products, asstated earlier, are kept in an oxygen-free atmosphere at all times.Preferably, due to availability and ease of use, an inert atmospheresuch as, for example, nitrogen, is the ambient.

Numerous chromium compounds can be prepared in accordance to theinvention, by varying the reactants and/or the quantity of each reactantemployed. The recovered, novel chromium compound or compounds can beused for olefin trimerization and/or polymerization without furtherpurification.

Optionally, the chromium compound can be purified in accordance with anymethod known in the art. For example, one of the simplest purificationprocedures is to wash the recovered solid with a non-polar organicsolvent such as, for example, toluene. Preferably, a non-polar aliphaticorganic solvent is used for best results. Exemplary wash solventsinclude, but are not limited to, pentane, hexane, cyclohexane, heptane,and mixtures thereof. Most preferably, pentane is the wash solvent.

The inventive chromium compounds can be used as a supported and/orunsupported catalyst for olefin trimerization and/or polymerization. Asupported chromium catalyst can be prepared according to any methodknown in the art. Any support useful to support chromium catalyst can beused. Exemplary catalyst supports include, but are not limited to,inorganic oxides, either alone or in combination, phosphated inorganicoxides, and mixtures thereof. Particularly preferred are supportsselected from the group consisting of silica, silica-alumina, alumina,fluorided alumina, silated alumina, thoria, aluminophosphate, aluminumphosphate, phosphated silica, phosphated alumina, silica-titania,coprecipitated silica/titania, and mixtures, thereof, fluorided/silatedalumina, being presently preferred, as well as any one or more of thesesupports which can contain chromium. The presently most preferredcatalyst support is because of the greatest trimerization activity, isaluminophosphate, as disclosed in U.S. Pat. No. 4,364,855 (1982), hereinincorporated by reference.

The supported chromium catalyst system can be prepared according to anymethod known in the art. For example, the reaction mixture, whichpreferably has been filtered to remove any particulate reactionby-products and contains one or more of the novel chromium pyrrolidecompounds, is combined and thoroughly contacted with a catalyst support.Excess electron pair donor solvent, such as, for example an ether, doesnot have to be removed prior to contacting the catalyst support.However, a solid chromium pyrrolide compound can be re-dissolved in anelectron pair donor solvent, such as, for example an ether, if desired.The chromium pyrrolide/ether solution is usually a blue or blue/greencolor, although other colors can be observed.

The catalyst support usually is insoluble in the ether/chromiumpyrrolide complex solution. Any excess of the chromium pyrrolide inrelation to the catalyst support is sufficient. However, usually, atleast about 5 grams of chromium pyrrolide compound per gram of catalystsupport is sufficient. Preferably about 0.001 to about 1 grams ofchromium pyrrolide compound per gram of support, and most preferablyabout 0.01 to about 0.5 grams of chromium pyrrolide compound per gram ofsupport is used for best support loading and most efficient use of thereagents. This mixture can be contacted and mixed at any time,temperature, and pressure to thoroughly contact the chromium pyrrolidecompound and support. For ease of use, ambient temperatures andpressures are preferred. Mixing times can be up to about 24 hours,preferably about 5 seconds to about 10 hours, and most preferably about5 seconds to about 8 hours. Longer times usually provide no additionalbenefit and shorter times can be insufficient for thorough contacting.

After the support is added and thoroughly combined with the chromiumpyrrolide it is collected by filtration, vacuum dried, then anactivating compound, usually as a solution of one or more Lewis acidsand/or metal alkyls, preferably in a hydrocarbon solvent, is added tothe support/chromium pyrrolide mixture. As used in this disclosure, aLewis acid is defined as any compound that is an electron acceptor.Preferably, the activating compound is a compound that can be consideredboth a Lewis acid and a metal alkyl. Preferred activating compoundswhich are both a metal alkyl and a Lewis acid include, but are notlimited to, alkylaluminum compounds, and mixtures thereof. The mostpreferred alkylaluminum compound is triethylaluminum, for best resultsin catalyst activity.

The hydrocarbon solvent can be any hydrocarbon that will dissolve theLewis acid. Preferred hydrocarbons include, but are not limited to,aromatic compounds having from about 6 to about 50 carbon atoms permolecule. Most preferably, the hydrocarbon solvent is toluene, for easeof removal and minimal interference with the resultant catalyst.

Any amount of activating compounds, such as a metal alkyl and/or a Lewisacid is sufficient to activate and/or react with the chromium pyrrolidecatalyst. Usually about 200 grams of Lewis acid per gram of chromium canbe used. Preferably, about 1 to about 100 grams of activating compound,such as a metal alkyl and/or a Lewis acid per gram of chromiumpyrrolide, and most preferably about 5 to about 30 grams of activatingcompound, such as a metal alkyl and/or a Lewis acid per gram of chromiumpyrrolide are used, for best catalyst activity. However, the amount ofLewis acid employed can vary with the catalyst support used. Forexample, if the support is silica and/or alumina, too much activatingcompound, such as a metal alkyl and/or a Lewis acid can decreasecatalyst activity. However, a similar amount of activating compound,such as a metal alkyl and/or a Lewis acid used with an aluminophosphatesupport does not always significantly decrease catalyst activity.

As disclosed earlier, the mixture of chromium pyrrolide, catalystsupport, and activating compound, such as a metal alkyl and/or a Lewisacid are mixed and/or contacted under a dry, inert atmosphere at alltimes. Any pressure can be used during the contacting; for ease of use,atmospheric pressure is preferred. Any temperature can be used duringthe contacting; for ease of use, room temperature, or ambienttemperature, is preferred. Some care should be taken during the mixing,so as not to destroy the physical integrity of the chromium pyrrolide,catalyst support, and resultant supported catalyst. The three-componentmixture can be contacted for any amount of time sufficient to prepareand activate a chromium catalyst. Usually times in the the range ofabout one minute to about one week are sufficient. Preferably, times inthe range of about 30 minutes to about 24 hours are used, and mostpreferably times in the range of about one hour to about 12 hours areused. Too short of mixing times can result in incomplete contacting andtoo long of mixing times will not provide any additional catalyticbenefit.

An alternative, and presently preferred, method to produce a supportedcatalyst is to combine one or more solid, inventive chromium pyrrolidecompounds with a hydrocarbon solvent, a disclosed earlier, such as, forexample, toluene, and an activating compound, such as a metal alkyland/or a Lewis acid, as disclosed earlier, such as, for example,triethylaluminum. This mixture can be stirred for any time sufficient todissolve the chromium pyrrolide compound, at any pressure ortemperature. Usually, times of about one minute to about one week,preferably about one hour to about 24 hours, and most preferably withinthe range of about three hours to about 12 hours are used. For ease ofoperation, ambient temperatures and pressures are used. Usually, a brownsolution will result.

After the solution is sufficiently mixed, a support is added to thesolution and stirred to thoroughly contact the solution and support. Thequantity of support is any amount sufficient to support the chromiumpyrrolide compound. Generally, the amount of support necessary is thesame as that disclosed in the previous ememplary process. Any suitablepressure and temperature can be used, although ambient temperature andpressure are preferred for ease of use. Usually, the mixing and/orcontacting time is within the range of about 30 minutes to about oneweek, preferably from about 3 hours to about 48 hours. Most preferably,the mixing and/or contacting time is within the range of about 5 hoursto about 24 hours, to maximize efficiency and result in a thoroughlycontacted support.

The solution then can be filtered to recover a solid catalytic product.The catalytic product, as with the reactants and reactions, ispreferably kept under an inert atmosphere to maintain chemicalstability.

If the chromium compound, such as, for example, a chromium pyrrolide, isrecovered and is to be used as an unsupported trimerization and/orpolymerization catalyst, olefins can be trimerized or polymerized in apresence of one or more of the inventive homogeneous chromium compounds,a saturated hydrocarbon as a diluent, and Lewis acid. Optionally,hydrogen can be added to the reactor to accelerate the reaction.

Reactants

Reactants applicable for use in polymerization with the catalyst andprocesses of this invention are olefinic compounds which can polymerize,i.e., react the same or with other olefinic compounds. Catalyst of theinvention can be used to polymerize at least one linear or branchedmono-1-olefin having about 2 to about 8 carbon atoms. Exemplarycompounds include, but are not limited to, ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.

Reactants applicable for use in the trimerization process, i.e., thecombination of any three olefins, of this invention are olefiniccompounds which can a) self-react, i.e., trimerize, to give usefulproducts such as, for example, the self reaction of ethylene can giveone hexene; and/or b) olefinic compounds which can react with otherolefinic compounds, i.e., co-trimerize, to give useful products such as,for example, co-trimerization of ethylene plus hexene can give onedecene and/or 1-tetradecene, co-trimerization of ethylene and 1-butenegives one octene, or 1-decene and ethylene can give 1-tetradecene and/or1-docosene. As used herein, the term "trimerization" is intended toinclude "co-trimerization" as defined above.

Suitable trimerizable olefinic compounds are those compounds having fromabout 2 to about 30 carbon atoms per molecule and having at least oneolefinic double bond. Exemplary compounds include, but are not limitedto acyclic and cyclic olefins such as, for example, ethylene, propylene,1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene,2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, and mixtures of any two or morethereof. If branched and/or cyclic olefins are used as reactants, whilenot wishing to be bound by theory, it is believed that steric hindrancecould hinder the trimerization process. Therefore, the branched and/orcyclic portion(s) of the olefin should be distant from the carbon-carbondouble bond.

The reaction products, i.e., trimers and/or polymers, can be preparedfrom the catalyst systems of this invention by solution reactions,slurry reactions, and/or gas phased reaction techniques usingconventional equipment and contacting processes. Contacting of themonomer or monomers with the catalyst system can be effected by anymanner known in the art of solid catalyst. One convenient method is tosuspend the catalyst system in an organic medium and to agitate themixture to maintain the catalyst system in suspension throughout thetrimerization and/or polymerization process. Other known contactingmethods such as fluidized bed, gravitating bed, and fixed bed can alsobe employed. Optionally, hydrogen can be added to the reactor toaccelerate the reaction.

The catalyst systems of this invention are particularly suitable for usein slurry trimerization and/or polymerizations. The slurry process isgenerally carried out in an inert diluent (medium), such as a paraffin,cycloparaffin, or aromatic hydrocarbon. One exemplary reactor diluent isisobutane. When the reactant is predominately ethylene, a temperature inthe range of about 60° to about 110° C. is employed.

Products

The olefinic and/or polymeric products of this invention haveestablished utility in a wide variety of applications such as, forexample, as monomers for use in the preparation of homopolymers,copolymers, and/or terpolymers. The polymeric products of this inventionhave established utility in a wide variety of applications such as forexample, polyethylene.

The further understanding of the present invention and its advantageswill be provided by reference to the following examples.

EXAMPLES Preparation of Chromium-Containing Compounds

Manipulations of all reactants were carried out either in a dryboxemploying nitrogen, or in airless glassware employing vacuum ornitrogen. Tetrahydrofuran (THF), toluene, benzene, diethylbenzene(Aldrich, 97% mixture of 1,2-, 1,3-, 1,4-isomers) and pentane werepurified by distillation over sodiumbenzophenone ketyl under nitrogen,then degassed via a nitrogen purge. Dimethoxyethane (DME) (Aldrich,anhydrous) was degassed via nitrogen purge and used without furtherpurification. Pyrrole (Aldrich, 98%) was vacuum distilled over sodium,then degassed via nitrogen purge. 2,5-Dimethylpyrrole was dried withcalcium sulfate and vacuum distilled. Sodium 2,5-dimethylpyrrolide (NaC₆H₈ N) was prepared by reacting 2,5-dimethylpyrrole with an excess ofsodium (40% by weight dispersion in mineral spirits) in refluxingtetrahydrofuran under nitrogen. Sodium pyrrolide was prepared byreacting pyrrole with an equivalent molar amount (1:1) of NaH (Aldrich,60% by weight in mineral oil) or sodium (40% dispersion by weight inmineral spirits) in dimethoxyethane or tetrahydrofuran (THF) at ambienttemperature under nitrogen. Triethylaluminum (TEA) (Aldrich 1.0M,hexanes and 1.9M toluene) was used as received. Ketjen Grade B alumina(Al₂ O₃) and Davison 952 silica (SiO₂) were the commercial materialsused as supports for catalyst preparations. Fluorided-alumina (F/Al₂ O₃,15 wt % F) was prepared by the addition of a solution of NH₄ HF₂ inmethanol to Ketjen Grade B alumina. Phosphated silica (P/SiO₂, P/Simolar ratio=0.1) was prepared by the addition of a 10% H₃ PO₄ /methanolsolution to Davison 952 silica. The aluminophosphate (AlPO₄) used in thefollowing experiments was made as described in McDaniel et al, U.S. Pat.No. 4,364,855 (1982). The supports were activated by placing up to 25 ginto a fritted quartz tube, fluidizing with air and calcining at 700°C., except for P/SiO₂ at 350° C., for 3 hours. The air stream wasswitched to nitrogen until the support cooled to ambient temperature.

Chromium pyrrolide complexes were typically prepared from anhydrouschromium (II or III) chloride and sodium pyrrolide as follows:

A typical synthetic procedure useful to prepare chromium pyrrolidecomplexes was that of reacting the chromium chlorides with sodiumpyrrolide (NaC₄ H₄ N, also referred to as NaPy) in refluxingtetrahydrofuran (THF). A molar reactant stoichiometry of 1CrCl₂ and2NaPy resulted in the isolation of a polymeric material, Product II, asthe major product and a pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀(OC₄ H₈)₄), as the minor product, see Equation 1. Using molar excess ofNaPy resulted in the isolation of the dianionic square planar complex{Cr(NC₄ H₄)₄ }{Na}₂.20OC₄ H₈, Product III, and the octahedral complex{Cr(C₄ H₄ N)₅ (OC₄ H₄)}{Na}₂ 4OC₄ H₈, Product IV, see Equation 2. Eachof the products was isolated through precipitation, Product II, orcrystallization, Products I, III, IV, from THF solutions by the additionof pentane. ##STR1##

EXAMPLE I

To prepare the pentanuclear complex, Product I, (Cr₅ (NC₄ H₄)₁₀ (OC₄H₈)₄), and the polymeric material, Product II, chromous chloride (2.0g/16.27 mmole) was combined with sodium pyrrolide (33.68 mmole) intetrahydrofuran and refluxed 20 hours. The reaction mixture was filtered(medium porosity frit) and the filtrate was used for fractionalcrystallization of both (Cr₅ (NC₄ H₄)₁₀ (OC₄ H₈)₄), Product I, and thepolymeric material, Product II, through the addition of pentane. Thepolymeric material crystallized as a blue solid followed by (Cr₅ (NC₄H₄)₁₀ (OC₄ H₈)₄) as opaque dark blue/purple crystals.

Analysis calculated for C₅₆ H₇₂ N₁₀ Cr₅, Product I: C, 55.62; H, 6.00;N, 11.58%, by weight. Found: C, 55.46; H, 6.32; N, 11.15%, by weight.Analysis found for Product II: Cr, 11.5; C, 59.75; H, 7.61; N, 9.17%, byweight, but variable upon precipitation conditions. An x-ray crystalstructure of Product I showed a pentanuclear complex incorporatingbridging amido-pyrrolyl, terminal amido-pyrrolyl, and tetrahydrofuranligands (FIGS. 1 and 2).

EXAMPLE II

To prepare {Cr(NC₄ H₄)₄ }{Na}₂. 2OC₄ H₈, Product III, and {Cr(C₄ H₄ N)₅(OC₄ H₈)}{Na}₂.4OC₄ H₈, Product IV, chromous chloride (3.0 g/24.4 mmole)was combined with sodium pyrrolide (100.9 mmole) in tetrahydrofuran andrefluxed 2 hours, see Equation 2. The reaction mixture was filtered(medium porosity frit) and the filtrate was used for fractionalcrystallization of both {Cr(NC₄ H₄)₄ }{Na}₂.2OC₄ H₈, Product III, and{Cr(C₄ H₄ N)₅ (OC₄ H₈)}{Na}₂. 4OC₄ H₈, Product IV, through the additionof pentane. Product III crystallized as translucent orange/red crystalsfollowed by Product IV as translucent purple crystals. While not wishingto be bound by theory, the formation of Product IV is believed to resultfrom the presence of chromic chloride in the chromous chloride reagent(Alfa, chromium (II) chloride, anhydrous, contains 5- 10% by weightCrCl₃) used in the preparation.

Analysis calculated for C₂₄ H₃₂ N₄ O₂ CrNa₂, Product III: C, 56.94; H,6.32; N, 11.07% by weight. Found: C, 57.04; H, 6.30; N, 10.92%, byweight. Analysis calculated for C₄₀ H₆₀ N₅ O₅ CrNa₂, Product IV: C,60.90; H, 7.67; N, 8.88% by weight. Found: C, 60.81; H, 7.74; N, 9.44%,by weight. An x-ray crystal structure of Product III showed a squareplanar complex incorporating terminal amido-pyrrolyl ligands (FIG. 4).An x-ray crystal structure of Product IV showed an octahedral complexincorporating terminal amido-pyrrolyl and a tetrahydrofuran ligand(FIGS. 5 and 6).

EXAMPLE III

The reaction product obtained from sodium pyrrolide and CrCl₃ was themost preferred in the preparation of an active catalyst. Pyrrole (7.0ml/100.9 mmole) was mixed with NaH (4.2 g of 60%, about 105 mmole) indimethoxyethane at ambient temperature until bubbling ceased. Chromicchloride (5.33 g/33.7 mmole) was added to the solution at ambienttemperature. The reaction mixture was refluxed under nitrogen for fivehours, see Equation 3. This resulted in a dark green solution. Thesolution was filtered (medium porosity frit) and stripped of solventunder vacuum and pumped dry under vacuum for 12 hours. The resultantchromium pyrrolide complex was a green solid, Product V. It was used inthe preparation of an active catalyst without further purification.##STR2##

EXAMPLE IV

All single crystal x-ray structure analyses were performed byCrystalytics Company, Lincoln, Nebr. Examples IV, V, VI, and IX containthe resultant analytical and subsequently computer-generated data.

A single crystal x-ray structure was obtained for [Cr₅ (NC₄ H₄)₁₀ (OC₄H₈)₄ ], Product I, and shown in FIGS. 1 and 2. The description of thesingle-crystal sample and amounting used for the collection are asfollows:

Color: Dark blue

Shape: Rectangular parallelepiped

Dimensions: 0.20×0.48×0.80 mm

Crystal Mount: Crystal was sealed inside a thin-walled glass capillarywith epoxy under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at half-height from ω Scans: 0.38°

The space group and cell data are as follows:

Crystal System: Triclinic

Space Group and Number:² P1-C_(i) ¹ (No. 2)

Number of Computer-Centered Reflections Used in the Least-Squares

Refinement of the Cell Dimensions: 15 20°>25°, °C.=20°±1°

Lattice Constants with esd's:

    ______________________________________                                        a = 10.803(2)Å                                                                         α = 85.59(2)°                                                                 V = 1407.9(6)Å.sup.3                            b = 9.825(2)Å                                                                          β = 96.23(2)°                                                                  Z = 1                                               c = 14.212(4)Å                                                                         γ = 109.99(2)°                                                                λ = 0.71073Å                             ______________________________________                                    

Molecular Weight: 1209.24 amu

Calculated Density: 1.427 g/cm⁻¹

Linear Absorption Coefficient:^(3a) 0.96 mm⁻¹

Tables I-V list the resultant parameters used to generate the molecularstructures shown in FIGS. 1 and 2.

                  TABLE I                                                         ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a                                    Equivalent Isotropic                                Atom   Fractional Coordinates                                                                           Thermal Parameter,                                  Type.sup.b                                                                           10.sup.4 x                                                                             10.sup.4 y                                                                             10.sup.4 z                                                                           B, Å.sup.2  × 10.sup.c              ______________________________________                                        Cr.sub.1                                                                             0.sup.d  0.sup.d  0.sup.d                                                                              25(1)                                         Cr.sub.2                                                                             636(1)   2281(1)  1500(1)                                                                              24(1)                                         Cr.sub.3                                                                             -1179(1) 841(1)   3122(1)                                                                              28(1)                                         N.sub.1a                                                                             -1155(3) 935(3)   715(2) 25(1)                                         C.sub.1a                                                                             -2195(4) 64(4)    1231(3)                                                                              31(1)                                         C.sub.2a                                                                             -3313(4) 390(5)   965(3) 41(1)                                         C.sub.3a                                                                             -3014(4) 1486(5)  257(3) 43(1)                                         C.sub.4a                                                                             -1728(4) 1791(4)  116(3) 34(1)                                         N.sub.1b                                                                             1566(3)  1902(3)  331(2) 29(1)                                         C.sub.1b                                                                             1753(4)  3095(4)  -308(3)                                                                              36(1)                                         C.sub.2b                                                                             3035(5)  3751(5)  -432(3)                                                                              51(2)                                         C.sub.3b                                                                             3736(4)  2986(5)  131(3) 51(2)                                         C.sub.4b                                                                             2823(4)  1865(4)  587(3) 38(1)                                         N.sub.1c                                                                             -320(3)  2997(3)  2480(2)                                                                              27(1)                                         C.sub.1c                                                                             375(4)   3732(4)  3273(3)                                                                              34(1)                                         C.sub.2c                                                                             29(5)    4919(4)  3383(3)                                                                              43(1)                                         C.sub.3c                                                                             -908(5)  4967(4)  2631(3)                                                                              42(1)                                         C.sub.4c                                                                             -1105(4) 3809(4)  2101(3)                                                                              32(1)                                         N.sub.1d                                                                             443(3)   350(3)   2743(2)                                                                              28(1)                                         C.sub.1d                                                                             1600(4)  715(4)   3289(3)                                                                              36(1)                                         C.sub.2d                                                                             2321(4)  -133(5)  3102(3)                                                                              46(2)                                         C.sub.3d                                                                             1567(5)  -1070(5) 2403(3)                                                                              46(2)                                         C.sub.4d                                                                             422(4)   -763(4)  2203(3)                                                                              36(1)                                         N.sub.1e                                                                             -1972(3) -1122(3) 3801(2)                                                                              35(1)                                         C.sub.1e                                                                             -1344(5) -2107(4) 4069(3)                                                                              41(1)                                         C.sub.2e                                                                             -2189(5) -3307(4) 4503(3)                                                                              44(1)                                         C.sub.3e                                                                             -3361(5) -3061(4) 4531(3)                                                                              47(1)                                         C.sub.4e                                                                             -3206(5) -1731(4) 4097(3)                                                                              47(1)                                         O.sub.1f                                                                             2351(3)  3985(3)  1883(2)                                                                              32(1)                                         C.sub.1f                                                                             3536(4)  4018(4)  2483(3)                                                                              43(1)                                         C.sub.2f                                                                             4470(6)  5479(6)  2336(5)                                                                              76(2)                                         C.sub.3f                                                                             3642(5)  6408(5)  2147(4)                                                                              62(2)                                         C.sub.4f                                                                             2396(4)  5463(4)  1635(3)                                                                              40(1)                                         O.sub.1g                                                                             -2551(3) 1543(3)  3659(2)                                                                              35(1)                                         C.sub.1g                                                                             -3763(4) 1733(5)  3232(3)                                                                              44(1)                                         C.sub.2g                                                                             -4097(5) 2625(6)  3907(4)                                                                              57(2)                                         C.sub.3g                                                                             -3524(5) 2241(6)  4845(3)                                                                              57(2)                                         C.sub.4g                                                                             -2319(5) 1977(6)  4633(3)                                                                              50(2)                                         ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1.                            .sup.c This is onethird of the trace of the orthogonalized B.sub.1j           tensor.                                                                       .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE II                                                        ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms                          in Crystalline [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.    4 ].sup.a,b                                                                   Atom  Anisotropic Thermal Parameter (Å.sup.4 × 10)                  Type.sup.c                                                                          B.sub.11                                                                              B.sub.22                                                                              B.sub.33                                                                            B.sub.12                                                                             B.sub.13                                                                              B.sub.23                           ______________________________________                                        Cr.sub.1                                                                            20(1)   23(1)   32(1)  5(1)  5(1)    -4(1)                              Cr.sub.2                                                                            23(1)   22(1)   27(1)  7(1)  3(1)    -2(1)                              Cr.sub.3                                                                            27(1)   26(1)   34(1) 11(1)  8(1)     1(1)                              N.sub.1a                                                                            21(1)   27(1)   29(1)  8(1)  1(1)    -2(1)                              C.sub.1a                                                                            28(2)   31(2)   30(2)  4(1)  8(1)    -4(1)                              C.sub.2a                                                                            23(2)   49(2)   49(2)  8(2)  5(2)    -16(2)                             C.sub.3a                                                                            31(2)   51(2)   52(2) 22(2)  -7(2)   -11(2)                             C.sub.4a                                                                            36(2)   32(2)   34(2) 15(1)  -2(1)   -3(1)                              N.sub.1b                                                                            24(1)   25(1)   35(1)  3(1)  5(1)    -4(1)                              C.sub.1b                                                                            40(2)   31(2)   33(2)  2(1)  11(1)   -1(1)                              C.sub.2b                                                                            46(2)   42(2)   54(2) -7(2)  24(2)   -5(2)                              C.sub.3b                                                                            25(2)   50(2)   71(3) -3(2)  15(2)   -27(2)                             C.sub.4b                                                                            29(2)   38(2)   48(2) 10(1)  0(2)    -15(2)                             N.sub.1c                                                                            28(1)   25(1)   30(1) 11(1)  3(1)    -2(1)                              C.sub.1c                                                                            36(2)   35(2)   31(2) 10(1)  4(1)    -3(1)                              C.sub.2c                                                                            52(2)   34(2)   43(2) 13(2)  6(2)    -13(1)                             C.sub.3c                                                                            51(2)   31(2)   50(2) 22(2)  5(2)    -5(2)                              C.sub.4c                                                                            35(2)   34(2)   31(2) 16(1)  4(1)     1(1)                              N.sub.1d                                                                            32(1)   23(1)   31(1) 12(1)  6(1)     3(1)                              C.sub.1d                                                                            33(2)   32(2)   42(2)  9(1)  6(2)    -0(1)                              C.sub.2d                                                                            36(2)   50(2)   59(2) 24(2)  6(2)     11(2)                             C.sub.3d                                                                            61(3)   44(2)   47(2) 36(2)  11(2)    3(2)                              C.sub.4d                                                                            49(2)   35(2)   31(2) 23(2)  4(2)     1(1)                              N.sub.1e                                                                            36(2)   30(1)   42(2) 13(1)  14(1)    4(1)                              C.sub.1e                                                                            46(2)   36(2)   46(2) 20(2)  10(2)    6(2)                              C.sub.2e                                                                            64(3)   30(2)   37(2) 15(2)  7(2)     4(1)                              C.sub.3e                                                                            55(3)   31(2)   46(2) -1(2)  18(2)   -0(2)                              C.sub.4e                                                                            39(2)   38(2)   62(2)  9(2)  17(2)    4(2)                              O.sub.1f                                                                            29(1)   25(1)   40(1)  6(1)  -1(1)   -2(1)                              C.sub.1f                                                                            34(2)   44(2)   45(2)  9(2)  -8(2)   -6(2)                              C.sub.2f                                                                            45(3)   67(3)   95(4) -3(2)  -15(3)  -6(3)                              C.sub.3f                                                                            59(3)   34(2)   78(3) -2(2)  -6(3)   -9(2)                              C.sub.4f                                                                            45(2)   23(1)   48(2)  7(1)  6(2)    -1(1)                              O.sub.1g                                                                            34(1)   41(1)   37(1) 19(1)  7(1)    -1(1)                              C.sub.1g                                                                            31(2)   56(2)   50(2) 20(2)  4(2)    -5(2)                              C.sub.2g                                                                            47(3)   65(3)   72(3) 35(2)  2(2)    -12(2)                             C.sub.3g                                                                            60(3)   75(3)   50(2) 36(2)  16(2)   -8(2)                              C.sub.4g                                                                            45(2)   77(3)   35(2) 27(2)  8(2)    -5(2)                              ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIG. 1.                       

                  TABLE III                                                       ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a          Atom        Fractional Coordinates                                            Type.sup.b  10.sup.4 x                                                                            10.sup.4 y 10.sup.4 z                                     ______________________________________                                        H.sub.1a    -2129   -661       1707                                           H.sub.2a    -4154   -55        1219                                           H.sub.3a    -3608   1937       -69                                            H.sub.4a    -1267   2508       -339                                           H.sub.1b    1053    3405       -617                                           H.sub.2b    3405    4593       -834                                           H.sub.3b    4676    3202       189                                            H.sub.4b    3031    1158       1020                                           H.sub.1c    1013    3445       3687                                           H.sub.2c    364     5592       3881                                           H.sub.3c    -1331   5685       2512                                           H.sub.4c    -1704   3580       1540                                           H.sub.1d    1881    1460       3743                                           H.sub.2d    3177    -88        3396                                           H.sub.3d    1807    -1790      2120                                           H.sub.4d    -291    -1252      1752                                           H.sub.1e    -446    -1976      3968                                           H.sub.2e    -1997   -4161      4742                                           H.sub.3e    -4139   -3699      4803                                           H.sub.4e    -3678   -1286      4012                                           H.sub.1fa   3351    3836       3136                                           H.sub.1fb   3882    3308       2299                                           H.sub.2fa   5068    5771       2893                                           H.sub.2fb   4965    5524       1806                                           H.sub.3fa   3462    6711       2728                                           H.sub.3fb   4068    7245       1757                                           H.sub.4fa   2417    5653       964                                            H.sub.4fb   1641    5625       1839                                           H.sub.1ga   -3631   2231       2623                                           H.sub.1gb   -4455   813        3162                                           H.sub.2ga   -5037   2381       3901                                           H.sub.2gb   -3704   3640       3750                                           H.sub.3ga   -4129   1385       5124                                           H.sub.3gb   -3307   3025       5266                                           H.sub.4ga   -2173   1220       5050                                           H.sub.4gb   -1565   2846       4703                                           ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 or sp.sup.3 hybridization of the        carbon atoms and a C--H bond length of 0.96Å) "riding" on their           respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded                              .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additional literal subscript (a      or b) where necessary to distinguish between hydrogen atoms bonded to the     same carbon.                                                             

                  TABLE IV                                                        ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline [Cr.sub.5 (NC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4      ].sup.a                                                                       Type.sup.b                                                                              Length, Å                                                                              Type.sup.b                                                                             Length, Å                                 ______________________________________                                        Cr.sub.1 . . . Cr.sub.2                                                                 3.066(1)     O.sub.1f --C.sub.1f                                                                    1.451(5)                                      Cr.sub.2 . . . Cr.sub.3                                                                 3.121(1)     O.sub.1f --C.sub.4f                                                                    1.453(5)                                                             O.sub.1g --C.sub.1g                                                                    1.448(6)                                      Cr.sub.1 --N.sub.1a                                                                     2.153(3)     O.sub.1g --C.sub.4g                                                                    1.451(5)                                      Cr.sub.1 --N.sub.1b                                                                     2.092(3)                                                            Cr.sub.2 --N.sub.1a                                                                     2.178(3)     C.sub.1a --C.sub.2a                                                                    1.360(6)                                      Cr.sub.2 --N.sub.1b                                                                     2.149(3)     C.sub.2a --C.sub.3a                                                                    1.395(6)                                      Cr.sub.2 --N.sub.1c                                                                     2.112(4)     C.sub.3a --C.sub.4a                                                                    1.351(6)                                      Cr.sub.3 --N.sub.1c                                                                     2.172(3)     C.sub.1b --C.sub.2b                                                                    1.338(6)                                      Cr.sub.3 --N.sub.1d                                                                     2.101(4)     C.sub.2b --C.sub.3b                                                                    1.393(7)                                      Cr.sub.3 --N.sub.1e                                                                     2.037(3)     C.sub.3b --C.sub.4b                                                                    1.376(6)                                                             C.sub.1c --C.sub.2c                                                                    1.365(7)                                      Cr.sub.2 --O.sub.1f                                                                     2.082(2)     C.sub.2c --C.sub.3c                                                                    1.400(6)                                      Cr.sub.3 --O.sub.1g                                                                     2.068(3)     C.sub.3c --C.sub.4c                                                                    1.356(6)                                                             C.sub.1d --C.sub.2d                                                                    1.376(7)                                      N.sub.1a --C.sub.1a                                                                     1.399(4)     C.sub.2d --C.sub.3d                                                                    1.396(6)                                      N.sub.1a --C.sub.4a                                                                     1.397(5)     C.sub.3d --C.sub.4d                                                                    1.367(8)                                      N.sub.1b --C.sub.1b                                                                     1.398(5)     C.sub.1e --C.sub.2e                                                                    1.370(5)                                      N.sub.1b --C.sub.4b                                                                     1.379(6)     C.sub.2e --C.sub.3e                                                                    1.374(8)                                      N.sub.1c --C.sub.1c                                                                     1.388(4)     C.sub.3e --C.sub.4e                                                                    1.366(6)                                      N.sub.1c --C.sub.4c                                                                     1.394(6)                                                            N.sub.1d --C.sub.1d                                                                     1.349(5)     C.sub.1f --C.sub.2f                                                                    1.460(6)                                      N.sub.1d --C.sub.4d                                                                     1.377(5)     C.sub.2f --C.sub.3f                                                                    1.474(9)                                      N.sub.1e --C.sub.1e                                                                     1.370(6)     C.sub.3f --C.sub.4f                                                                    1.496(6)                                      N.sub.1e --C.sub.4e                                                                     1.361(6)     C.sub.1g --C.sub.2g                                                                    1.496(8)                                                             C.sub.2g --C.sub.3g                                                                    1.485(7)                                                             C.sub.3g --C.sub.4g                                                                    1.476(9)                                      ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1.                       

                  TABLE V                                                         ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in Crystalline                        [Cr.sub.5 (MC.sub.4 H.sub.4).sub.10 (OC.sub.4 H.sub.8).sub.4 ].sup.a          Type.sup.b                                                                             Angle, deg    Type.sup.b                                                                              Angle, deg                                   ______________________________________                                        N.sub.1a Cr.sub.1 N.sub.1b                                                             84.8(1)       Cr.sub.1 N.sub.1a Cr.sub.2                                                               90.2(1)                                     N.sub.1a Cr.sub.1 N.sub.1a'.sup.c                                                      180.0(-).sup.d                                                                              Cr.sub.1 N.sub.1a C.sub.1a                                                              121.2(2)                                     N.sub.1b Cr.sub.1 N.sub.1a'.sup.c                                                      95.2(1)       Cr.sub.2 N.sub.1a C.sub.1a                                                              118.0(2)                                     N.sub.1b Cr.sub.1 N.sub.1b'.sup.c                                                      180.0(-).sup.d                                                                              Cr.sub.1 N.sub.1a C.sub.4a                                                              113.4(2)                                                            Cr.sub.2 N.sub.1a C.sub.4a                                                              110.6(2)                                     N.sub.1a Cr.sub.2 N.sub.1b                                                             82.9(1)       C.sub.1a N.sub.1a C.sub.4a                                                              103.5(3)                                     N.sub.1a Cr.sub.2 N.sub.1c                                                             96.5(1)       Cr.sub.1 N.sub.1b Cr.sub.2                                                               92.6(1)                                     N.sub.1b Cr.sub.2 N.sub.1c                                                             168.9(1)      Cr.sub.1 N.sub.1b C.sub.1b                                                              117.9(2)                                     N.sub.1a Cr.sub.2 O.sub.1f                                                             162.4(1)      Cr.sub.2 N.sub.1b C.sub.1b                                                              107.6(3)                                     N.sub.1b Cr.sub.2 O.sub.1f                                                             89.5(1)       Cr.sub.1 N.sub.1b C.sub.4b                                                              120.6(3)                                     N.sub.1c Cr.sub.2 O.sub.1f                                                             87.9(1)       Cr.sub.2 N.sub.1b C.sub.4b                                                              113.0(3)                                                            C.sub.1b N.sub.1b C.sub.4b                                                              104.4(3)                                     N.sub.1c Cr.sub.3 N.sub.1d                                                             88.1(1)       Cr.sub.2 N.sub.1c Cr.sub.3                                                               93.5(1)                                     N.sub.1c Cr.sub.3 N.sub.1e                                                             176.5(1)      Cr.sub.2 N.sub.1c C.sub.1c                                                              121.4(3)                                     N.sub.1d Cr.sub.3 N.sub.1e                                                             93.5(1)       Cr.sub.3 N.sub.1c C.sub.1c                                                              100.0(2)                                     N.sub.1c Cr.sub.3 O.sub.1g                                                             88.8(1)       Cr.sub.2 N.sub.1c C.sub.4c                                                              116.1(2)                                     N.sub.1d Cr.sub.3 O.sub.1g                                                             170.4(1)      Cr.sub.3 N.sub.1c C.sub.4c                                                              121.5(2)                                     N.sub.1e Cr.sub.3 O.sub.1g                                                             89.1(1)       C.sub.1c N.sub.1c C.sub.4c                                                              104.2(3)                                                            Cr.sub.3 N.sub.1d C.sub.1d                                                              121.3(3)                                     N.sub.1a C.sub.1a C.sub.2a                                                             110.6(3)      Cr.sub.3 N.sub.1d C.sub.4d                                                              127.8(3)                                     C.sub.1a C.sub.2a C.sub.3a                                                             107.5(4)      C.sub.1d N.sub.1d C.sub.4d                                                              106.4(4)                                     C.sub.2a C.sub.3a C.sub.4a                                                             106.9(4)      Cr.sub.3 N.sub.1e C.sub.1e                                                              126.3(3)                                     C.sub.3a C.sub.4a N.sub.1a                                                             111.5(3)      Cr.sub.3 N.sub.1e C.sub.4e                                                              128.3(3)                                     N.sub.1b C.sub.1b C.sub.2b                                                             111.2(4)      C.sub.1e N.sub.1e C.sub.4e                                                              105.3(3)                                     C.sub.1b C.sub.2b C.sub.3b                                                             107.4(4)                                                             C.sub.2b C.sub.3b C.sub.4b                                                             107.0(4)      Cr.sub.2 O.sub.1f C.sub.1f                                                              131.5(2)                                     C.sub.3b C.sub.4b N.sub.1b                                                             110.1(4)      Cr.sub.2 O.sub.1f C.sub.4f                                                              118.9(2)                                     N.sub.1c C.sub.1c C.sub.2c                                                             110.9(4)      C.sub.1f O.sub.1f C.sub.4f                                                              109.1(3)                                     C.sub.1c C.sub.2c C.sub.3c                                                             106.8(4)      Cr.sub.3 O.sub.1g C.sub.1g                                                              131.9(3)                                     C.sub.2c C.sub.3c C.sub.4c                                                             107.2(4)      Cr.sub.3 O.sub.1g C.sub.4g                                                              118.6(3)                                     C.sub.3c C.sub.4c N.sub.1c                                                             110.9(3)      C.sub.1g O.sub.1g C.sub.4g                                                              109.5(4)                                     N.sub.1d C.sub.1d C.sub.2d                                                             110.3(4)                                                             C.sub.1d C.sub.2d C.sub.3d                                                             106.7(4)      O.sub.1f C.sub.1f C.sub.2f                                                              105.0(4)                                     C.sub.2d C.sub.3d C.sub.4d                                                             106.6(5)      C.sub.1f C.sub.2f C.sub.3f                                                              104.9(4)                                     C.sub.3d C.sub.4d N.sub.1d                                                             109.9(3)      C.sub.2f C.sub.3f C.sub.4f                                                              104.4(4)                                     N.sub.1e C.sub.1e C.sub.2e                                                             110.0(4)      C.sub.3f C.sub.4f O.sub.1f                                                              105.4(4)                                     C.sub.1e C.sub.2e C.sub.3e                                                             107.2(4)      O.sub.1g C.sub.1g C.sub.2g                                                              104.8(4)                                     C.sub.2e C.sub.3e C.sub.4e                                                             106.7(4)      C.sub.1g C.sub.2g C.sub.3g                                                              104.2(5)                                     C.sub.3e C.sub.4e N.sub.1e                                                             110.8(5)      C.sub.2g C.sub.3g C.sub.4g                                                              104.2(4)                                                            C.sub.3g C.sub.4g O.sub.1g                                                              106.1(4)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 1                             .sup.c Atoms labeled with a prime () are related to nonprimed atoms by th     symmetry operation x, y, z where the fractional coordinates (x, y, z) are     given in Table I.                                                             .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

EXAMPLE V

A single crystal x-ray structure was obtained for Cr(NC₄ H₄)₄, a portionof Product III and shown in FIG. 3. A single crystal x-ray structure wasobtained for [Na]₂ [Cr(NC₄ H₄)₄ ].2(OC₄ H₈), Product III and shown inFIG. 4. The description of the single-crystal sample and mounting usedfor the data collection are as follows:

Color: Red-Orange

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.65 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.86°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² C2/c - C_(2h) ⁶ (no. 15)

Number of Computer-Centered Reflections Used in the Least-SquaresRefinement of the Cell Dimensions:

Dimensions: 15 20°>25°, °C.=20°+1°

Lattice Constants with esd's:

    ______________________________________                                        a = 9.522(2)Å                                                                           α = 90.00°                                                                    V = 2697(1)Å.sup.3                             b = 15.118(2)Å                                                                          β = 98.99(1)°                                                                  Z = 4                                              c = 18.967(3)Å                                                                          γ = 90.00°                                                                    λ = 0.71073Å                            ______________________________________                                    

Molecular Weight: 506.52 amu

Calculated Density: 1.248 g/cm⁻³

Linear Absorption Coefficient:^(3a) 0.47 mm⁻¹

Tables VI-X list the resultant parameters used to generate the molecularstructures shown in FIGS. 3 and 4.

                  TABLE VI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }--2(OC.sub.4 H.sub.8).sup.a                                     Equivalent Isotropic                                Atom   Fractional Coordinates                                                                           Thermal Parameter,                                  Type.sup.b                                                                           10.sup.4 x                                                                             10.sup.4 y                                                                             10.sup.4 z                                                                           B, Å.sup.2 × 10.sup.c               ______________________________________                                        Anion                                                                         Cr      0.sup.d 2982(1)  2500.sup.d                                                                           50(1)                                         N.sub.1                                                                              1901(4)  2924(2)  3183(2)                                                                              56(1)                                         N.sub.2                                                                              ).sup.d  4343(3)  2500.sup.d                                                                           52(1)                                         N.sub.3                                                                              0.sup.d  1612(3)  2500.sup.d                                                                           70(2)                                         C.sub.11                                                                             3241(5)  2950(3)  3000(3)                                                                              65(2)                                         C.sub.12                                                                             4224(6)  2769(3)  3587(3)                                                                              73(2)                                         C.sub.13                                                                             3513(7)  2630(4)  4146(3)                                                                              82(2)                                         C.sub.14                                                                             2094(7)  2734(4)  3884(3)                                                                              76(2)                                         C.sub.21                                                                             907(5)   4884(3)  2926(3)                                                                              60(1)                                         C.sub.22                                                                             582(4)   5753(3)  2766(3)                                                                              69(2)                                         C.sub.31                                                                             390(5)   1081(3)  1996(4)                                                                              94(2)                                         C.sub.32                                                                             236(7)   213(3)   2189(5)                                                                              133(6)                                        Cation                                                                        Na     2301(2)  6079(1)  1783(1)                                                                              69(1)                                         Solvent of Crystallization                                                    O.sub.1                                                                              2065(4)  5108(2)  830(2) 83(1)                                         C.sub.41                                                                             2759(11) 5174(5)  239(4) 143(4)                                        C.sub.42                                                                             2804(11) 4319(5)  -79(4) 148(4)                                        C.sub.43                                                                             1893(10) 3786(5)  264(5) 142(4)                                        C.sub.44                                                                             1699(9)  4231(4)  902(4) 120(3)                                        ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIGS. 3 and 4.                     .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                       .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE VII                                                       ______________________________________                                        Anisotropic Thermal Parameters 0.sup.Nonhydrogen                              Atoms in Crystalline                                                          {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }--2OC.sub.4 H.sub.8.sup.a,b           Atom  Anisotropic Thermal Parameter (Å.sup.2 × 10)                  Type.sup.c                                                                          B.sub.11 B.sub.22                                                                              B.sub.33                                                                             B.sub.12                                                                            B.sub.13                                                                             B.sub.23                           ______________________________________                                        Anion                                                                         Cr    64(1)    34(1)   55(1)   .sup.d                                                                             15(1)   0.sup.d                           N.sub.1                                                                             69(2)    44(2)   56(2)  6(1)  12(1)  6(1)                               N.sub.2                                                                             64(3)    39(2)   56(3)  0.sup.d                                                                             16(2)  0.sup.d                            N.sub.3                                                                             65(3)    38(2)   107(4) 0.sup.d                                                                             14(3)  0.sup.d                            C.sub.11                                                                            79(3)    50(2)   70(3)  -6(2) 18(2)  2(2)                               C.sub.12                                                                            70(3)    62(3)   84(3)  4(2)  7(2)   -8(2)                              C.sub.13                                                                            103(4)   79(3)   58(3)  22(3) -8(3)  8(2)                               C.sub.14                                                                            86(3)    86(3)   58(3)  16(3) 16(2)  5(2)                               C.sub.21                                                                            66(2)    45(2)   70(3)  -2(2) 15(2)  -6(2)                              C.sub.22                                                                            68(3)    38(2)   105(4) -7(2) 27(2)  -9(2)                              C.sub.31                                                                            65(3)    61(3)   152(5) 6(2)  9(3)   -36(3)                             C.sub.32                                                                            71(5)    46(2)   266(15)                                                                              6(3)  -20(6) -44(4)                             Cation                                                                        Na    70(1)    57(1)   81(1)  -2(1) 15(1)  -15(1)                             Solvent of Crystallization                                                    O.sub.1                                                                             100(2)   65(2)   82(2)  -10(2)                                                                              30(2)  -16(2)                             C.sub.41                                                                            222(8)   112(5)  116(5) -46(5)                                                                              92(6)  -22(4)                             C.sub.42                                                                            192(8)   160(8)  107(5) 12(6) 70(5)  -32(5)                             C.sub.43                                                                            147(6)   109(6)  177(8) -27(5)                                                                              48(6)  -69(6)                             C.sub.44                                                                            177(6)   77(4)   124(5) -21(4)                                                                              76(5)  -14(3)                             ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIGS. 3 and 4.                     .sup.d This is a symmetryrequired value and is therefore listed without a     estimated standard deviation.                                            

                  TABLE VIII                                                      ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                           (Na).sub. 2 {Cr(NC.sub.4 H.sub.4).sub.4 }--2(OC.sub.4 H.sub.8).sup.a         Atom     Fractional Coordinates                                               Type.sup.b                                                                             10.sup.4 x 10.sup.4 y 10.sup.4 z                                     ______________________________________                                        Anion                                                                         H.sub.11 3456       3081       2541                                           H.sub.12 5235       2748       3680                                           H.sub.13 3922       2488       4628                                           H.sub.14 1341       2679       4164                                           H.sub.21 1665       4687       3285                                           H.sub.22 1071       6262       2985                                           H.sub.31 706        1274       1565                                           H.sub.32 493        -301       1937                                           Solvent of Crystallization                                                    H.sub.41a                                                                              2250       5576       -100                                           H.sub.41b                                                                              3710       5388       385                                            H.sub.42a                                                                              3756       4091       -1                                             H.sub.42b                                                                              2464       4348       -583                                           H.sub.43a                                                                              995        3707       -39                                            H.sub.43b                                                                              2326       3220       377                                            H.sub.44a                                                                              2295       3973       1304                                           H.sub.44b                                                                              723        4191       969                                            ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 or sp.sup.3hybridization of the         carbon atoms and a C--H bond length of 0.96Å ) "riding" on their          respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded.                             .sup.b Hydrogen atoms are labeled with the same numerical subscripts as       the carbon atoms to which they are covalently bonded with an additional       literal subscript (a or b) where necessary to distinguish between             hydrogens bonded to the same carbon.                                     

                  TABLE IX                                                        ______________________________________                                        Anion Bond Lengths and Bond Angles Involving                                  Nonhydrogen Atoms in                                                          Crystalline {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }--2OC.sub.4 H.sub.8.su    p.a                                                                           ______________________________________                                        Type.sup.b Length, Å                                                                            Type.sup.b Length, Å                                ______________________________________                                        Cr--N.sub.1                                                                              2.057(3)   C.sub.11 --C.sub.12                                                                      1.355(7)                                     Cr--N.sub.2                                                                              2.056(4)   C.sub.12 --C.sub.13                                                                      1.361(9)                                     Cr--N.sub.3                                                                              2.072(5)   C.sub.13 --C.sub.14                                                                      1.374(9)                                                           C.sub.21 --C.sub.22                                                                      1.372(6)                                     N.sub.1 --C.sub.11                                                                       1.369(7)   C.sub.22 --C.sub.22' .sup.c                                                              1.379(9)                                     N.sub.1 --C.sub.14                                                                       1.344(6)   C.sub.31 --C.sub.32                                                                      1.376(7)                                     N.sub.2 --C.sub.21                                                                       1.360(5)   C.sub.32 --C.sub.32' '.sup.c                                                             1.327(18)                                    N.sub.3 --C.sub.31                                                                       1.344(7)                                                           ______________________________________                                        Type.sup.b Angle, deg.                                                                              Type.sup.b Angle, deg.                                  ______________________________________                                        N.sub.1 CrN.sub.2                                                                        92.5(1)    N.sub.1 C.sub.11 C.sub.12                                                                110.5(5)                                     N.sub.1 CrN.sub.3                                                                        87.5(1)    C.sub.11 C.sub.12 C.sub.13                                                               107.3(5)                                     N.sub.1 CrN.sub.1' .sup.c                                                                175.1(2)   C.sub.12 C.sub.13 C.sub.14                                                               106.4(5)                                     N.sub.2 CrN.sub.3                                                                        180.0(-).sup.d                                                                           N.sub.1 C.sub.14 C.sub.13                                                                110.9(5)                                                           N.sub.2 C.sub.21 C.sub.22                                                                110.2(4)                                     CrN.sub.1 C.sub.11                                                                       127.5(3)   C.sub.21 C.sub.22 C.sub.22' .sup.c                                                       106.8(3)                                     CrN.sub.1 C.sub.14                                                                       127.1(4)   N.sub.3 C.sub.31 C.sub.32                                                                109.1(6)                                     C.sub.11 N.sub.1 C.sub.14                                                                104.9(4)   C.sub.31 C.sub.32 C.sub.32' .sup.c                                                       107.5(5)                                     CrN.sub.2 C.sub.21                                                                       127.0(2)                                                           C.sub.21 N.sub.2 C.sub.21' .sup.c                                                        106.0(5)                                                           CrN.sub.3 C.sub.31                                                                       126.7(3)                                                           C.sub.31 N.sub.3 C.sub.31' .sup.c                                                        106.7(6)                                                           ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 4.                            .sup.c Atoms labeled with a prime(') are related to nonprimed atoms by th     symmetry operation x,y,x.                                                

                  TABLE X                                                         ______________________________________                                        Bond Lengths and Angles Involving the Nonhydrogen Atoms                       of the Cation and Solvent of Crystallization in                               {Na}.sub.2 {Cr(NC.sub.4 H.sub.4).sub.4 }--2(OC.sub.4 H.sub.8).sup.a           ______________________________________                                        Type.sup.b Length, Å                                                                             Type.sup.b                                                                              Length, Å                                ______________________________________                                        Na--O.sub.1                                                                              2.313(4)    O.sub.1 --C.sub.41                                                                       1.390(10)                                                          O.sub.1 --C.sub.44                                                                      1.38(7)                                      Na . . . N.sub.1".sup.c                                                                  2.888(4)                                                           Na . . . N.sub.3".sup.c                                                                  2.830(4)    C.sub.41 --C.sub.42                                                                     1.43(1)                                                             C.sub.42 --C.sub.43                                                                     1.42(1)                                                             C.sub.43 --C.sub.44                                                                     1.42(1)                                      ______________________________________                                        Type.sup.b Angle, deg. Type.sup.b                                                                              Angle, deg.                                  ______________________________________                                        O.sub.1 NaN.sub.1".sup.c                                                                 128.6(3)    C.sub.41 O.sub.1 C.sub.44                                                               107.9(5)                                     O.sub.1 NaN.sub.3".sup.c                                                                 121.8(3)                                                           N.sub.1" NaN.sub.3".sup.c                                                                 59.9(3)    O.sub.1 C.sub.41 C.sub.42                                                               109.0(7)                                                            C.sub.41 C.sub.42 C.sub.43                                                              105.0(8)                                     NaO.sub.1 C.sub.41                                                                       125.7(4)    C.sub.42 C.sub.43 C.sub.44                                                              107.0(7)                                     NaO.sub.1 C.sub.44                                                                       121.8(4)    O.sub.1 C.sub.44 C.sub.43                                                               107.6(7)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 4.                            .sup.c Atoms labeled with a double prime(") are related to nonprimed atom     by the symmetry operation 1/2 - x, 1/2 + y, 1/2 - z.                     

EXAMPLE VI

Single crystal x-ray structures were obtained for [Cr(NC₄ H₄)₅ (OC₄H₈)], shown in FIG. 5, and [Cr(NC₄ H₄)₅ (OC₄ H₈)][Na]₂.4(OC₄ H₈),Product IV, and shown in FIG. 6. The description of the single-crystalsample and mounting used for data collection are as follows:

Color: Purple

Shape: Rectangular parallelepiped

Dimensions: 0.50×0.55×0.63 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longest edge nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.42°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² P2₁ -C₂ ² (No. 4)

Number of Computer-Centered Reflections Used in the Least-Squares

Refinement of the Cell Dimensions: 15 20°>20°, °C.=20±1°

Lattice Constants with esd's:

    ______________________________________                                        a = 10.042(2)Å                                                                          α = 90.00°                                                                     V = 2162(1)Å.sup.3                            b = 17.242(4)Å                                                                          β = 106.54(2)°                                                                  Z = 2                                             c = 13.025(3)Å                                                                          γ = 90.00°                                                                     λ = 0.71073Å                           ______________________________________                                    

Molecular Weight=788.93 amu

Calculated Density: 1.212 g/cn⁻³

Linear Absorption Coefficient:^(3a) 0.32 mm⁻¹

Tables XI-XV list the resultant parameters used to generate themolecular structures shown in FIGS. 5 and 6.

                  TABLE XI                                                        ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in Crystalline                       [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)][Na].sub.2 --4(OC.sub.4        H.sub.8).sup.a                                                                                           Equivalent Isotropic                               Atom  Fractional Coordinates                                                                             Thermal Parameter,                                 Type.sup.b                                                                          10.sup.4 x                                                                              10.sup.4 y                                                                             10.sup.4 z                                                                            B, Å.sup.2 × 10.sup.c              ______________________________________                                        Anion                                                                         Cr    198(1)    1477 .sup.                                                                             2531(1) 32(1)                                        N.sub.1a                                                                            1694(5)   2026(3)  2028(4) 40(2)                                        C.sub.1a                                                                            1749(7)   2782(4)  1742(6) 48(2)                                        C.sub.2a                                                                            2929(8)   2926(5)  1420(7) 66(3)                                        C.sub.3a                                                                            3661(7)   2236(5)  1554(6) 62(3)                                        C.sub.4a                                                                            2899(6)   1695(5)  1913(5) 52(2)                                        N.sub.1b                                                                            1651(5)   1087(3)  3885(4) 40(2)                                        C.sub.1b                                                                            1463(8)   560(4)   4575(5) 48(2)                                        C.sub.2b                                                                            2572(9)   518(6)   5423(8) 82(4)                                        C.sub.3b                                                                            3554(8)   1064(6)  5275(6) 70(3)                                        C.sub.4b                                                                            2952(6)   1382(5)  4340(5) 48(2)                                        N.sub.1c                                                                            -1326(5)  1888(3)  1250(4) 38(2)                                        C.sub.1c                                                                            -1200(8)  2172(4)  266(6)  51(2)                                        C.sub.2c                                                                            -2458(8)  2270(5)  -476(6) 58(3)                                        C.sub.3c                                                                            -3435(8)  2038(6)  56(7)   75(3)                                        C.sub.4c                                                                            -2710(7)  1826(5)  1091(6) 56(3)                                        N.sub.1d                                                                            -32(5)    2455(4)  3445(5) 43(2)                                        C.sub.1d                                                                            504(7)    2562(5)  4505(6) 49(2)                                        C.sub.2d                                                                            107(9)    3278(5)  4774(8) 72(3)                                        C.sub.3d                                                                            -698(8)   3629(5)  3832(6) 59(3)                                        C.sub.4d                                                                            -769(7)   3108(4)  3055(6) 52(2)                                        N.sub.1e                                                                            315(5)    505(4)   1690(4) 40(2)                                        C.sub.1e                                                                            -574(8)   277(5)   704(6)  55(3)                                        C.sub.2e                                                                            -197(10)  -432(5)  403(7)  67(3)                                        C.sub.3e                                                                            990(10)   -662(6)  1256(8) 79(4)                                        C.sub.4e                                                                            1265(8)   -92(4)   2016(7) 51(3)                                        O.sub.1f                                                                            -1356(4)  926(3)   3083(4) 43(1)                                        C.sub.1f                                                                            -2047(7)  1244(5)  3800(6) 57(3)                                        C.sub.2f                                                                            -3263(10) 713(6)   3706(9) 98(5)                                        C.sub.3f                                                                            -2833(11) -21(6)   3402(8) 93(4)                                        C.sub.4f                                                                            -1903(8)  171(5)   2724(7) 64(3)                                        Cation 1                                                                      Na.sub.1                                                                            2254(3)   3336(2)  3737(3) 75(1)                                        Cation 2                                                                      Na.sub.2                                                                            1430(3)   974(2)   126(2)  62(1)                                        Solvent Molecules of Crystallization                                          O.sub.1g                                                                            4576(6)   3329(4)  4706(5) 83(2)                                        C.sub.1g                                                                            5748(9)   3100(10) 4433(9) 125(6)                                       C.sub.2g                                                                            6723(12)  2831(11) 5281(9) 145(7)                                       C.sub.3g                                                                            6503(15)  3272(11) 6146(11)                                                                              204(8)                                       C.sub.4g                                                                            5037(14)  3498(11) 5737(10)                                                                              170(8)                                       O.sub.1h                                                                            2342(7)   4602(4)  3279(6) 97(3)                                        C.sub.1h                                                                            1316(11)  5151(7)  2894(10)                                                                              112(5)                                       C.sub.2h                                                                            2017(16)  5830(9)  2541(11)                                                                              153(7)                                       C.sub.3h                                                                            3180(12)  5561(10) 2425(10)                                                                              131(6)                                       C.sub.4h                                                                            3551(13)  4848(7)  3070(11)                                                                              115(6)                                       O.sub.1i                                                                            1391(7)   1752(4)  -1377(4)                                                                              80(2)                                        C.sub.i1                                                                            2235(19)  1594(11) -1998(13)                                                                             160(8)                                       C.sub.2i                                                                            2716(17)  2287(14) -2337(15)                                                                             165(10)                                      C.sub.3i                                                                            1991(28)  2906(11) -1934(14)                                                                             204(12)                                      C.sub.4i                                                                            1010(16)  2533(7)  -1523(9)                                                                              128(6)                                       O.sub.1j                                                                            3037(5)   155(4)   -264(5) 72(2)                                        C.sub.1j                                                                            4389(10)  48(7)    427(9)  113(5)                                       C.sub.2j                                                                            4998(16)  -571(10) -23(16) 174(8)                                       C.sub.3j                                                                            4001(11)  -840(8)  -1006(10)                                                                             127(6)                                       C.sub.4j                                                                            2728(11)  -493(7)  -974(8) 92(4)                                        ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIGS. 5 and 6.                     .sup.c This is onethird of the trace of the orthogonalized B.sub.1j           tensor.                                                                  

                  TABLE XII                                                       ______________________________________                                        Anisotropic Thermal Parameters Nonhydrogen Atoms in                           Crystalline [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)][Na].sub.2         --4(OC.sub.4 H.sub.8).sup.a,b                                                 Atom  Anisotropic Thermal Parameter (Å.sup.2 × 10)                  Type.sup.c                                                                          B.sub.11                                                                              B.sub.22 B.sub.33                                                                            B.sub.12                                                                             B.sub.13                                                                            B.sub.23                            ______________________________________                                        Anion                                                                         Cr    29(1)   31(1)    38(1) (1)    12(1) 1(1)                                N.sub.1a                                                                            33(2)   44(3)    44(3) -1(2)  11(2) 5(2)                                C.sub.1a                                                                            48(4)   37(3)    59(4) -0(3)  15(3) 3(3)                                C.sub.2a                                                                            55(4)   61(5)    90(5) -19(4) 34(4) 13(4)                               C.sub.3a                                                                            37(3)   82(6)    76(5) -9(3)  33(3) 2(4)                                C.sub.4a                                                                            40(3)   64(5)    52(4) 4(3)   16(3) -5(3)                               N.sub.1b                                                                            36(2)   44(3)    36(3) 7(2)   5(2)  12(2)                               C.sub.1b                                                                            52(4)   51(4)    40(3) -1(3)  9(3)  10(3)                               C.sub.2b                                                                            73(5)   85(6)    83(6) 2(5)   13(4) 44(5)                               C.sub.3b                                                                            51(4)   88(6)    54(4) 0(4)   -13(3)                                                                              12(4)                               C.sub.4b                                                                            41(3)   55(4)    45(3) 0(3)   5(2)  4(4)                                N.sub.1c                                                                            33(2)   41(3)    39(3) 4(2)   9(2)  1(2)                                C.sub.1c                                                                            52(4)   51(4)    51(4) 6(3)   16(3) 5(3)                                C.sub.2c                                                                            64(5)   62(5)    37(4) -1(4)  -4(3) 4(4)                                C.sub.3c                                                                            32(3)   92(6)    89(6) 4(4)   -3(4) 29(5)                               C.sub.4c                                                                            42(3)   78(5)    48(4) -1(3)  9(3)  14(4)                               N.sub.1d                                                                            31(2)   44(3)    56(3) 4(2)   13(2) -1(3)                               C.sub.1d                                                                            44(3)   60(5)    39(4) -5(3)  8(3)  -11(3)                              C.sub.2d                                                                            63(4)   70(6)    84(6) -11(4) 20(4) -47(5)                              C.sub.3d                                                                            69(4)   43(4)    73(5) 9(3)   32(4) -14(4)                              C.sub.4d                                                                            42(3)   53(4)    63(4) 8(3)   17(3) 3(4)                                N.sub.1e                                                                            47(3)   36(3)    39(3) - 3(2) 17(2) -7(2)                               C.sub.1e                                                                            59(4)   49(4)    53(4) -15(3) 11(3) -1(4)                               C.sub.2e                                                                            92(5)   48(4)    69(5) -20(4) 36(4) -26(4)                              C.sub.3e                                                                            91(6)   45(5)    106(7)                                                                              4(4)   37(5) -13(5)                              C.sub.4e                                                                            62(4)   23(3)    69(5) 7(3)   20(4) -7(3)                               O.sub.1f                                                                            40(2)   42(2)    51(2) -4(2)  20(2) 2(2)                                C.sub.1f                                                                            61(4)   64(5)    60(4) -2(3)  39(3) 4(4)                                C.sub.2f                                                                            81(6)   95(7)    144(8)                                                                              -24(5) 74(6) 1(6)                                C.sub.3f                                                                            109(7)  80(6)    117(7)                                                                              -26(5) 75(6) -3(6)                               C.sub.4f                                                                            61(4)   53(4)    85(5) -27(4) 30(4) -16(4)                              Cation 1                                                                      Na.sub.1                                                                            57(2)   71(2)    95(2) -13(1) 21(2) -2(2)                               Cation 2                                                                      Na.sub.2                                                                            68(2)   69(2)    56(2) -2(1)  30(1) -3(2)                               Solvent Molecules of Crystallization                                          O.sub.1g                                                                            58(3)   95(4)    92(4) -8(3)  15(3) -2(4)                               C.sub.1g                                                                            54(5)   215(14)  108(8)                                                                              0(7)   29(5) -7(9)                               C.sub.2g                                                                            96(7)   226(15)  121(9)                                                                              52(9)  43(7) 51(10)                              C.sub.3g                                                                            129(10) 277(19)  148(11)                                                                             52(12) -56(9)                                                                              -134(13)                            C.sub.4g                                                                            134(10) 250(18)  128(10)                                                                             44(11) 39(9) -89(11)                             O.sub.1h                                                                            71(4)   68(4)    152(6)                                                                              -8(3)  32(4) -3(4)                               C.sub.1h                                                                            92(7)   95(8)    144(9)                                                                              -2(6)  28(7) -3(7)                               C.sub.2h                                                                            212(14) 108(9)   140(10)                                                                             36(10) 50(10)                                                                              66(9)                               C.sub.3h                                                                            99(8)   175(14)  101(8)                                                                              -6(9)  -2(6) 32(9)                               C.sub.4h                                                                            99(8)   79(7)    168(11)                                                                             -13(6) 38(8) 29(8)                               O.sub.1i                                                                            98(4)   82(4)    73(3) 8(3)   47(3) 13(3)                               C.sub.1i                                                                            230(15) 128(11)  168(12)                                                                             8(11)  131(12)                                                                             74(10)                              C.sub.2i                                                                            112(10) 222(21)  156(15)                                                                             1(12)  28(10)                                                                              23(16)                              C.sub.3i                                                                            370(26) 124(12)  135(12)                                                                             -93(15)                                                                              99(15)                                                                              34(10)                              C.sub.4i                                                                            223(13) 81(7)    106(8)                                                                              32(8)  91(9) 31(6)                               O.sub. 1j                                                                           59(3)   64(3)    94(4) 5(3)   22(3) -21(3)                              C.sub.1j                                                                            88(7)   101(8)   133(9)                                                                              19(6)  2(6)  -58(7)                              C.sub.2j                                                                            94(8)   190(14)  205(13)                                                                             73(10) -11(9)                                                                              -90(13)                             C.sub.3j                                                                            83(7)   130(10)  160(10)                                                                             16(7)  20(7) -86(9)                              C.sub.4j                                                                            82(6)   104(8)   92(7) -7(6)  29(5) -41(6)                              ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the structure report.                                          .sup.c Atoms are labeled in agreement with FIGS. 5 and 6.                

                  TABLE XIII                                                      ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)][Na].sub.2 --4(OC.sub.4        N.sub.8).sup.a                                                                Atom     Fractional Coordinates                                               Type.sup.b                                                                             10.sup.4 x 10.sup.4 y 10.sup.4 z                                     ______________________________________                                        Anion                                                                         H.sub.1a 1061       3165       1756                                           H.sub.2a 3182       3406       1151                                           H.sub.3a 4547       2153       1428                                           H.sub.4a 3162       1162       2059                                           H.sub.1b 637        254        4479                                           H.sub.2b 2692       174        6022                                           H.sub.3b 4453       1179       5753                                           H.sub.4b 3373       1775       4016                                           H.sub.1c -326       2281       132                                            H.sub.2c -2637      2453       -1199                                          H.sub.3c -4426      2031       -243                                           H.sub.4c -3137      1655       1623                                           H.sub.1d 1070       2197       4997                                           H.sub.2d 349        3499       5480                                           H.sub.3d -1115      4135       3762                                           H.sub.4d -1278      3184       2317                                           H.sub.1e -1346      578        293                                            H.sub.2e -630       -712       -243                                           H.sub.3e 1503       -1135      1285                                           H.sub.4e 1999       -107       2676                                           H.sub.1fa                                                                              -1447      1250       4520                                           H.sub.1fb                                                                              -2359      1762       3588                                           H.sub.2fa                                                                              -4069      899        3170                                           H.sub.2fb                                                                              -3468      674        4380                                           H.sub.3fa                                                                              -2341      -312       4022                                           H.sub.3fb                                                                              -3620      -314       2996                                           H.sub.4fa                                                                              -2417      184        1980                                           H.sub.4fb                                                                              -1165      -201       2831                                           Solvent of Crystallization                                                    H.sub.1ga                                                                              6103       3536       4135                                           H.sub.1gb                                                                              5503       2694       3909                                           H.sub.2ga                                                                              6629       2283       5371                                           H.sub.2gb                                                                              7629       2940       5209                                           H.sub.3ga                                                                              6644       2947       6766                                           H.sub.3gb                                                                              7102       3717       6322                                           H.sub.4ga                                                                              4960       4045       5839                                           H.sub.4gb                                                                              4493       3223       6118                                           H.sub.1ha                                                                              596        4950       2301                                           H.sub.1hb                                                                              921        5310       3451                                           H.sub.2ha                                                                              2205       6231       3073                                           H.sub.2hb                                                                              1449       6034       1874                                           H.sub.3ha                                                                              3066       5447       1684                                           H.sub.3hb                                                                              3908       5936       2669                                           H.sub.4ha                                                                              4260       4953       3725                                           H.sub.4hb                                                                              3874       4459       2671                                           H.sub.1ia                                                                              3007       1289       -1594                                          H.sub.1ib                                                                              1721       1306       -2615                                          H.sub.2ia                                                                              3703       2328       -2031                                          H.sub.2ib                                                                              2496       2303       -3103                                          H.sub.3ia                                                                              1541       3249       -2509                                          H.sub.3ib                                                                              2638       3195       -1381                                          H.sub.4ia                                                                              101        2580       -2020                                          H.sub.4ib                                                                              1010       2761       -851                                           H.sub.1ja                                                                              4929       513        470                                            H.sub.1jb                                                                              4341       -91        1129                                           H.sub.2ja                                                                              5823       -388       -178                                           H.sub.2jb                                                                              5232       -992       479                                            H.sub.3ja                                                                              3930       -1396      -1018                                          H.sub.3jb                                                                              4261       -668       -1623                                          H.sub.4ja                                                                              2185       -862       -715                                           H.sub.4jb                                                                              2215       -324       -1678                                          ______________________________________                                         .sup.a Hydrogen atoms were included in the structure factor calculations      as idealized atoms (assuming sp.sup.2 -- or sp.sup.3 -- hybridization of      the carbon atoms and a C--H bond length of 0.96Å) "riding" on their       respective carbon atoms. The isotropic thermal parameter of each hydrogen     atom was fixed at 1.2 times the equivalent isotropic thermal parameter of     the carbon atom to which it is covalently bonded.                             .sup.b Hydrogen atoms are labeled with the same numerical and literal         subscripts as their carbon atoms with an additional literal subscript (a,     or b) where necessary to distinguish between hydrogen atoms bonded to the     same carbon.                                                             

                  TABLE XIV                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in Crystalline                       [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)][Na].sub.2 --4(OC.sub.4        H.sub.8).sup.a                                                                Type.sup.b Length, Å                                                                             Type.sup.b Length, Å                               ______________________________________                                        Cr--N.sub.1a                                                                             2.035(6)    Na.sub.1 --O.sub.1g                                                                      2.314(6)                                    Cr--N.sub.1b                                                                             2.056(5)    Na.sub.1 --O.sub.1h                                                                      2.271(8)                                    Cr--N.sub.1c                                                                             2.044(5)                                                           Cr--N.sub.1d                                                                             2.114(6)    Na.sub.2 --O.sub.1i                                                                      2.365(7)                                    Cr--N.sub.1e                                                                             2.024(6)    Na.sub.2 --O.sub.1j                                                                      2.307(7)                                    Cr--O.sub.1f                                                                             2.120(5)    C.sub.1g --C.sub.2g                                                                      1.33(2)                                                            C.sub.2g --C.sub.3g                                                                      1.43(2)                                     N.sub.1a --C.sub.1a                                                                      1.36(1)     C.sub.3g --C.sub.4g                                                                      1.47(2)                                     N.sub.1a --C.sub.4a                                                                      1.38(1)     C.sub.1h --C.sub.2h                                                                      1.51(2)                                     N.sub.1b --C.sub.1b                                                                      1.33(1)     C.sub.2h --C.sub.3h                                                                      1.30(2)                                     N.sub.1b --C.sub.4b                                                                      1.37(1)     C.sub.3h --C.sub.4h                                                                      1.48(2)                                     N.sub.1c --C.sub.1c                                                                      1,41(1)     C.sub.1i --C.sub.2i                                                                      1.41(3)                                     N.sub.1c --C.sub.4c                                                                      1.35(1)     C.sub.2i --C.sub.3i                                                                      1.47(3)                                     N.sub.1d --C.sub.1d                                                                      1.34(1)     C.sub.3i --C.sub.4i                                                                      1.40(3)                                     N.sub.1d --C.sub.4d                                                                      1.36(1)     C.sub.1j --C.sub.2j                                                                      1.44(2)                                     N.sub.1e --C.sub.1e                                                                      1.40(1)     C.sub.2j --C.sub.3j                                                                      1.46(2)                                     N.sub.1e --C.sub.4e                                                                      1.39(1)     C.sub.3j --C.sub.4j                                                                      1.42(2)                                     O.sub.1f --C.sub.1f                                                                      1.42(1)     O.sub.1g --C.sub.1g                                                                      1.38(1)                                     O.sub.1f --C.sub.4f                                                                      1.44(1)     O.sub.1g --C.sub.4g                                                                      1.32(1)                                                            O.sub.1h --C.sub.1h                                                                      1.38(1)                                     C.sub.1a --C.sub.2a                                                                      1.39(1)     O.sub.1h --C.sub.4h                                                                      1.39(2)                                     C.sub.2a --C.sub.3a                                                                      1.38(1)     O.sub.1i --C.sub.1i                                                                      1.36(2)                                     C.sub.3a --C.sub.4a                                                                      1.37(1)     O.sub.1i --C.sub.4i                                                                      1.40(1)                                     C.sub.1b --C.sub.2b                                                                      1.33(1)     O.sub.1j --C.sub.1j                                                                      1.41(1)                                     C.sub.2b --C.sub.3b                                                                      1.42(1)     O.sub.1j --C.sub.4j                                                                      1.43(1)                                     C.sub.3b --C.sub.4b                                                                      1.31(1)                                                            C.sub.1c --C.sub.2c                                                                      1.37(1)     Na.sub.1 --C.sub.1a                                                                      2.678(8)                                    C.sub.2c --C.sub.3c                                                                      1.41(1)     Na.sub.1 --N.sub.1d                                                                      2.688(7)                                    C.sub.3c --C.sub.4c                                                                      1.39(1)     Na.sub.1 --C.sub.1d                                                                      2.621(9)                                    C.sub.1d --C.sub.2d                                                                      1.37(1)                                                            C.sub.2d --C.sub.3d                                                                      1.40(1)                                                            C.sub.3d --C.sub.4d                                                                      1.34(1)     Na.sub.2 --C.sub.4a                                                                      2.681(7)                                    C.sub.1e --C.sub.2e                                                                      1.37(1)     Na.sub.2 --C.sub.1e                                                                      2.630(9)                                    C.sub.2e --C.sub.3e                                                                      1.43(1)                                                            C.sub.3e --C.sub.4e                                                                      1.37(1)                                                            C.sub.1f --C.sub.2f                                                                      1.50(1)                                                            C.sub.2f --C.sub.3f                                                                      1.43(2)                                                            C.sub.3f --C.sub.4f                                                                      1.49(2)                                                            ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 6.                       

                  TABLE XV                                                        ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in Crystalline                        [Cr(NC.sub.4 H.sub.4).sub.5 (OC.sub.4 H.sub.8)][Na].sub.2 --4(OC.sub.4        H.sub.8).sup.a                                                                Type.sup.b Angle, deg Type.sup.b Angle, deg                                   ______________________________________                                        N.sub.1a CrN.sub.1b                                                                       91.2(2)   O.sub.1g Na.sub.1 O.sub.1h                                                                 92.3(3)                                    N.sub.1a CrN.sub.1c                                                                       91.4(2)   O.sub.1g Na.sub.1 C.sub.1a                                                                114.3(3)                                    N.sub.1a CrN.sub.1d                                                                       91.1(2)   O.sub.1g Na.sub.1 N.sub.1d                                                                139.6(3)                                    N.sub.1a CrN.sub.1e                                                                       92.8(2)   O.sub.1g Na.sub.1 C.sub.1d                                                                118.0(3)                                    N.sub.1a CrO.sub.1f                                                                      178.7(2)   O.sub.1h Na.sub.1 C.sub.1a                                                                 95.6(3)                                    N.sub.1b CrN.sub.1c                                                                      176.2(2)   O.sub.1h Na.sub.1 N.sub.1d                                                                127.0(2)                                    N.sub.1b CrN.sub.1d                                                                       86.7(2)   O.sub.1h Na.sub.1 C.sub.1d                                                                132.1(3)                                    N.sub.1b CrN.sub.1e                                                                       93.3(2)   C.sub.1a Na.sub.1 N.sub.1d                                                                 75.1(2)                                    N.sub.1b CrO.sub.1f                                                                       88.5(2)   C.sub.1a Na.sub.1 C.sub.1d                                                                103.1(3)                                    N.sub.1c CrN.sub.1d                                                                       90.4(2)   N.sub.1d Na.sub.1 C.sub.1d                                                                 29.3(2)                                    N.sub.1c CrN.sub.1e                                                                       89.4(2)                                                           N.sub.1c CrO.sub.1f                                                                       88.8(2)   O.sub.1i Na.sub.2 O.sub.1j                                                                 90.7(3)                                    N.sub.1d CrN.sub.1e                                                                      176.1(2)   O.sub.1i Na.sub.2 C.sub.4a                                                                109.3(3)                                    N.sub.1d CrO.sub.1f                                                                       87.6(2)   O.sub.1i Na.sub.2 C.sub.1e                                                                131.5(2)                                    N.sub.1e CrO.sub.1f                                                                       88.5(2)   O.sub.1j Na.sub.2 C.sub.4a                                                                103.2(2)                                                          O.sub.1j Na.sub.2 C.sub.1e                                                                115.1(3)                                    CrN.sub.1a C.sub.1a                                                                      128.7(5)   C.sub.4a Na.sub.2 C.sub.1e                                                                103.9(3)                                    CrN.sub.1a C.sub.4a                                                                      126.3(5)                                                           CrN.sub.1b C.sub.1b                                                                      127.0(4)   Na.sub.1 O.sub.1g C.sub.1g                                                                131.4(6)                                    CrN.sub.1b C.sub.4b                                                                      127.3(5)   Na.sub.1 O.sub.1g C.sub.4g                                                                124.0(8)                                    CrN.sub.1c C.sub.1c                                                                      128.5(5)   Na.sub.1 O.sub.1h C.sub.1h                                                                132.2(7)                                    CrN.sub.1c C.sub.4c                                                                      126.7(5)   Na.sub.1 O.sub.1h C.sub.4h                                                                116.6(6)                                    CrN.sub.1d C.sub.1d                                                                      127.7(5)   Na.sub.2 O.sub.1i C.sub.1i                                                                120.9(8)                                    CrN.sub.1d C.sub.4d                                                                      125.7(5)   Na.sub.2 O.sub.1i C.sub.4i                                                                126.8(7)                                    CrN.sub.1e C.sub.1e                                                                      127.7(5)   Na.sub.2 O.sub.1j C.sub.1j                                                                123.1(6)                                    CrN.sub.1e C.sub.4e                                                                      126.2(4)   Na.sub.2 O.sub.1j C.sub.4j                                                                125.8(5)                                    CrO.sub.1f C.sub.1f                                                                      126.4(4)   C.sub.1g O.sub.1g C.sub.4g                                                                104.3(8)                                    CrO.sub.1f C.sub.4f                                                                      123.1(5)   C.sub.1h O.sub.1h C.sub.4h                                                                108.9(9)                                                          C.sub.1i O.sub.1i C.sub.4i                                                                107.8(11)                                   C.sub.1a N.sub. 1a C.sub.4a                                                              105.0(6)   C.sub.1j O.sub.1j C.sub.4j                                                                107.7(7)                                    C.sub.1b N.sub.1b C.sub.4b                                                               105.2(5)                                                           C.sub.1c N.sub.1c C.sub.4c                                                               104.0(5)   O.sub.1g C.sub.1g C.sub.2g                                                                111(1)                                      C.sub.1d N.sub.1d C.sub.4d                                                               106.6(6)   C.sub.1g C.sub.2g C.sub.3g                                                                103(1)                                      C.sub.1e N.sub.1e C.sub.4e                                                               106.0(6)   C.sub.2g C.sub.3g C.sub.4g                                                                103(1)                                                            C.sub.3g C.sub.4g O.sub.1g                                                                110(1)                                      C.sub.1f O.sub.1f C.sub.4f                                                               110.5(6)   O.sub.1h C.sub.1h C.sub.2h                                                                106(1)                                                            C.sub.1h C.sub.2h C.sub.3h                                                                106(1)                                      N.sub.1a C.sub.1a C.sub.2a                                                               111.1(7)   C.sub.2h C.sub.3h C.sub.4h                                                                109(1)                                      C.sub.1a C.sub.2a C.sub.3a                                                               106.1(8)   C.sub.3h C.sub.4h O.sub.1h                                                                106(1)                                      C.sub.2a C.sub.3a C.sub.4a                                                               107.5(7)   O.sub.1i C.sub.1i C.sub.2i                                                                110(2)                                      C.sub.3a C.sub.4a N.sub.1a                                                               110.3(7)   C.sub.1i C.sub.2i C.sub.3i                                                                105(2)                                      N.sub.1b C.sub.1b C.sub.2b                                                               110.6(7)   C.sub.2i C.sub.3i C.sub.4i                                                                106(2)                                      C.sub.1b C.sub.2b C.sub.3b                                                               107.6(8)   C.sub.3i C.sub.4i O.sub.1i                                                                107(1)                                      C.sub.2b C.sub.3b C.sub.4b                                                               104.4(7)   O.sub.1j C.sub.1j C.sub.2j                                                                106(1)                                      C.sub.3b C.sub.4b N.sub.1b                                                               112.2(7)   C.sub.1j C.sub. 2j C.sub.3j                                                               109(1)                                      N.sub.1c C.sub.1c C.sub.2c                                                               112.4(7)   C.sub.2j C.sub.3j C.sub.4j                                                                104(1)                                      C.sub.1c C.sub.2c C.sub.3c                                                               104.5(7)   C.sub.3j C.sub.4j O.sub.1j                                                                108(1)                                      C.sub.2c C.sub.3c C.sub.4c                                                               107.8(7)                                                           C.sub.3c C.sub.4c N.sub.1c                                                               111.2(7)   Na.sub.1 C.sub.1a N.sub.1a                                                                 95.0(4)                                    N.sub.1d C.sub.1d C.sub.2d                                                               109.0(7)   Na.sub.1 C.sub.1a C.sub.2a                                                                106.7(5)                                    C.sub.1d C.sub.2d C.sub.3d                                                               107.6(8)   Na.sub.1 N.sub.1d Cr                                                                      107.7(3)                                    C.sub.2d C.sub.3d C.sub.4d                                                               105.4(8)   Na.sub.1 N.sub.1d C.sub.1d                                                                 72.6(4)                                    C.sub.3d C.sub.4d N.sub.1d                                                               111.5(7)   Na.sub.1 N.sub.1d C.sub.4d                                                                 86.4(4)                                    N.sub.1e C.sub.1e C.sub.2e                                                               111.0(7)   Na.sub.1 C.sub.1d N.sub.1d                                                                 78.1(4)                                    C.sub.1e C.sub.2e C.sub.3e                                                               105.2(7)   Na.sub.1 C.sub.1d C.sub.2d                                                                 85.1(6)                                    C.sub.2e C.sub.3e C.sub.4e                                                               108.4(8)                                                           C.sub.3e C.sub.4e N.sub.1e                                                               109.5(7)   Na.sub.2 C.sub.4a N.sub.1a                                                                 90.2(3)                                                          Na.sub.2 C.sub.4a C.sub.3a                                                                104.0(5)                                    O.sub.1f C.sub.1f C.sub.2f                                                               104.4(7)   Na.sub.2 C.sub.1e N.sub.1e                                                                 78.1(4)                                    C.sub.1f C.sub.2f C.sub.3f                                                               105.0(9)   Na.sub.2 C.sub.1e C.sub.2e                                                                 91.7(6)                                    C.sub.2f C.sub.3f C.sub.4f                                                               104.9(9)                                                           C.sub.3f C.sub.4f O.sub.1f                                                               104.7(7)                                                           ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 6.                       

EXAMPLE VII

The product obtained from the reaction of sodium 2,5-dimethylpyrrolideand CrCl₂ used in the preparation of an active catalyst was a light bluesolid, Product VI. 2,5-Dimethylpyrrole (5.0 ml/49.1 mmole) was mixedwith excess sodium (40% dispersion in mineral spirits) intetrahydrofuran (125 ml) at ambient temperature. The mixture wasrefluxed 12 hours under nitrogen then filtered to remove excess sodium.The sodium 2,5-dimethylpyrrolide was used in-site and combined withchromous chloride (3.03 g/24.7 mmole) at ambient temperature. Thereaction mixture was refluxed under nitrogen for 48 hours. Thegray-green solution was filtered (medium porosity frit) at ambienttemperature and stripped of solvent under vacuum, then pumped dry undervacuum for 12 hours resulting in a gray/green solid. This gray/greensolid was then washed with pentane resulting in a light blue solid,Product VI, which was collected by filtration. Product VI was used inthe preparation of an active catalyst without further purification.

EXAMPLE VIII Preparation of Catalysts

All polymerization runs were carried out in a two liter reactor underslurry (particle form) conditions. The diluent was isobutane and thereactor temperature was 90° C. Reactor pressure held at 550 psig duringthe polymerization, with ethylene being fed on demand.

The actual charging of the reactor was accomplished by the followingmethod. After purging the reactor at 100° C. with a stream of nitrogenfor at least 15 minutes, the reactor temperature was lowered to 90° C.and a preweighed amount of supported chromium pyrrolide catalyst wascharged against a slight countercurrent of nitrogen. One liter ofisobutane was then charge to the reactor and finally the reactorpressurized with ethylene.

The ethylene consumed was determined using a precalibrated ethylene flowmeter. Samples of the liquid product mixture were taken after 30 minuterun time without depressurizing the reactor. This was done by filling to200-300 psig a steel sampling cylinder adapted to the reactor with a diptube fitted with a fritted tip extending into the bottom of the reactorvessel. Samples taken this way were analyzed by gas chromatography andgas chromatography-mass spectrometry. Selectivities were normalized to100%. Solid products were obtained by venting the reactor to atmosphere,separating by decantation of the liquids from the solid material. Thesolids were then dried at 100° C. in a vacuum oven and weighed. Theyield of solid product was obtained by weighing the combined solid andcatalyst residues and subtracting from this the preweighed catalystcharge. The yield of volatile products was obtained by subtracting theyield of solid products from the grams of ethylene consumed as recordedby the flow meter.

Activity typically ranged from 300-1500 g product/g catalyst/hourcalculated for 30 minute run time, as shown in Table XVI. The productobtained typically was represented by 97-99.5% by weight liquids and0.5-3% by weight polymer (wax). The liquid fraction was typically 85%hexenes, 11% decenes, 2% tetradecences, based on the total weight of theliquid fraction. The balance of the liquid product mixture was a tracelevel distribution of olefins typically totaling about 1-2% by weight ofthe product mixture, see Table XVII.

Active catalysts were prepared from the chromium pyrrolide complexes asfollows. All toluene and/or pentane rinses used about 15 to about 30 mlsof liquid.

Run 1: 0.158 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 9.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 24 hours.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (2.00 g) was added to the solution and stirred for anadditional 24 hours. The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.3143 g of the catalyst was charged directly to thereactor for polymerization. 1.0 ml of a 0.5% TEA in heptanes solutionwas charged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

Run 2: 0.081 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml diethylbenzene at ambient temperature. 2.0 ml of a1M TEA in hexanes solution was added to the solution and stirred for 24hours. The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al moleratio=0.4) (1.50 g) was added to the solution and stirred for anadditional 1 hour. The supported catalyst was filtered from the solutionas a brown solid, rinsed twice with dimethylbenzene, and then twice withpentane. 0.4333 g of the catalyst was charged directly to the reactorfor polymerization. 3.0 ml of a 0.5% TEA in heptanes solution wascharged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

Run 3: 0.093 g of Product V (prepared in DME solvent) was slurried with15 ml toluene at ambient temperature. 5.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.1564 g of thecatalyst was charged directly to the reactor for polymerization. 3.0 mlof a 0.5% TEA in heptanes solution was charged to the reactor after thecatalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 4: 0.080 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 6.0 ml of a 1M TEA in hexanessolution was added and the solution stirred for 16 hours. The formationof a brown solution and the complete dissolution of Product I resultedimmediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.50 g) wasadded to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice pentane. 1.1988 g of thecatalyst was charged directly to the reactor for polymerization.

Run 5: 0.079 g of Product II (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 2.0 ml of a 1.9M TEA in toluenesolution was added to the solution and stirred for 8 hours. Theformation of a brown solution and the complete dissolution of Product IIresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4)(0.50 g) was added to the solution and stirred for an additional 16hours. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. 0.4829 gof the catalyst was charged directly to the reactor for polymerization.

Run 6: 0.071 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 2.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 1 hour.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. SiO₂ (2.52 g) wasadded to the solution and stirred for an additional 2 minutes. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. All of thecatalyst was charged directly to the reactor for polymerization.

Run 7: 0.103 g of Product II (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 1.0 ml of a 1.9M TEA in toluenesolution was added to the solution and stirred for 10 minutes. Theformation of a brown solution and the complete dissolution of Product IIresulted immediately upon TEA addition. Al₂ O₃ (2.27 g) was added to thesolution and stirred for an additional 2 minutes. The supported catalystwas filtered from the solution as a brown solid, rinsed twice withtoluene, and then twice with pentane. 1.2926 g of the catalyst wascharged directly to the reactor for polymerization.

Run 8: 0.120 g of Product I (prepared in THF solvent) was slurried with15 ml toluene at ambient temperature. 2.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 2 days. The formationof a brown solution and the complete dissolution of Product I resultedimmediately upon TEA addition. SiO₂ (1.0 g) was added to the solutionand stirred for an additional 3 weeks. The supported catalyst wasfiltered from the solution as a brown solid, rinsed twice with toluene,and then twice with pentane. All of the catalyst was charged directly tothe reactor for polymerization.

Run 9: 0.106 g of Product III (prepared in THF solvent) was slurriedwith 15 ml toluene at ambient temperature. 2.5 ml of a 1.9M TEA intoluene solution was added to the solution and stirred for 2 hours. Theformation of a brown solution and the complete dissolution of ProductIII resulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4)(0.65 g) was added to the solution and stirred for an additional 2hours. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. All ofthe catalyst was charged directly to the reactor for polymerization. 1.5ml of a 1.0% TEA in pentane solution was charged to the reactor afterthe catalyst charge but before the isobutane (reactor solvent) charge topurge feedstock poisons.

Run 10: 0.030 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml toluene at ambient temperature. 3.0 ml of a 1M TEAin hexanes solution was added to the solution and stirred for 16 hours.The formation of a brown solution and the complete dissolution ofProduct V resulted immediately upon TEA addition. AlPO₄ (P/Al=0.9) (2.0g) was added to the solution and stirred for an additional 16 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with toluene, and then twice with pentane. 0.322/g ofcatalyst was charged directly to the reactor for polymerization.

Run 11: 0.067 g of Product V (prepared in THF solvent) was slurried with15 ml pentane at ambient temperature. 4.0 ml of a 1M TEA in hexanessolution was added to the solution and stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for an additional 24 hours. Thesupported catalyst was filtered from the solution as a brown solid,rinsed twice with pentane. All of the catalyst was charged directly tothe reactor for polymerization. 3.0 ml of a 0.5% TEA in heptanessolution was charged to the reactor after the catalyst charge but beforethe isobutane (reactor solvent) charge to purge feedstock poisons.

Run 12: 0.073 g of Product V (prepared in THF solvent), which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF, wasslurried with 15 ml toluene at ambient temperature. 6.0 ml of a 1M TEAin hexanes solution was added and the solution stirred for 24 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. P/SiO₂ (7.0 g) was added to thesolution and stirred for an additional 24 hours which nearly decolorizedit. The supported catalyst was filtered from the solution as a brownsolid, rinsed twice with toluene, and then twice with pentane. 2.85 g ofcatalyst was charged directly to the reactor for polymerization.

Run 13: 0.125 g or Product II was slurried with 15 ml diethylbenzene atambient temperature. 9.0 ml of a 1M TEA in hexane solution was added tothe solution and stirred for 8 hours. The formation of a brown solutionand the complete dissolution of Product II resulted immediately upon TEAaddition. F/Al₂ O₃ (2.0 g) was added to the solution and stirred for anadditional 12 hours. The supported catalyst was filtered from thesolution as a brown solid, rinsed twice with toluene, and then twicewith pentane. 0.5477 g of catalyst was charged directly to the reactorfor polymerization.

Run 14: 0.125 g of Product VI was slurried with 15 ml toluene at ambienttemperature. 1.5 ml of a 1M TEA in hexanes solution was added and thesolution stirred for 10 minutes. The formation of a red/brown solutionand the complete dissolution of Product VI resulted immediately upon TEAaddition. SiO₂ (2.0 g) was added to the solution and stirred for anadditional 1 minute which nearly decolorized it. The supported silicacatalyst was filtered from the solution as a red/brown solid, rinsedtwice with toluene, and then twice with pentane. All of the catalyst wascharged directly to the reactor for polymerization.

Run 15: 0.30 g of Product V (prepared in DME solvent) was dissolved with15 ml of dimethoxyethane forming a green solution. This solution wasthen mixed with 0.6 g of AlPO₄ (P/Al₄ mole ratio=0.4) (2.00 g) and themixture was stirred 1 hour. The green supported material was filteredfrom the solution, rinsed with dimethoxyethane and dried with a nitrogenpurge at 90° C. This material was then stirred with 15 ml of toluene and3 ml of triethylaluminum (Aldrich 1.0M, hexanes) for an additional 3hours. The brown supported catalyst was collected by filtration, rinsedwith pentane, and dried under vacuum. 0.4609 g of the catalyst wascharged directly to the reactor for polymerization. 3.0 ml of a 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge but before the isobutane (reactor solvent) charge to purgefeedstock poisons.

Run 16: 0.058 g of Product V (prepared in THF solvent) which was heatedto 80° C. for 4 hours under nitrogen flush to remove residual THF wasslurried with 15 ml benzene at ambient temperature. 4.0 ml of a 1M TEAin hexanes solution was added and the solution stirred for 2 hours. Theformation of a brown solution and the complete dissolution of Product Vresulted immediately upon TEA addition. AlPO₄ (P/Al mole ratio=0.4) (1.0g) was added to the solution and stirred for 1 hour. The supportedcatalyst was filtered from the solution as a brown solid, rinsed twicewith benzene, and then twice with pentane. All of the catalyst wascharged directly to the reactor for polymerization. 3.0 ml of a 0.5% TEAin heptanes solution was charged to the reactor after the catalystcharge but before the isobutane (reactor solvent) charge to purgefeedstock poisons.

Run 17: 0.1610 g of Product I was charged directly to the reactor at 90°C. The reactor was charged with 1 liter isobutane and pressurized to 550psig with ethylene. No ethylene consumption was detected, therefore 50psig of dihydrogen was charged to the reactor which did not initiateethylene consumption. Ethylene consumption was initiated after 2.0 ml of1M TEA in hexane solution was charged.

Run 18: 0.3528 g of Product VI was charged directly to the reactor at90° C. The reactor was charged with 1 liter isobutane and pressurized to550 psig with ethylene. No ethylene consumption was detected, therefore2.0 ml of a 1M TEA in hexanes solution was charged which did initiateethylene consumption.

Run 19: 0.3482 g of Product VI was charged directly to the reactor at90° C. The reactor was also charged with 2.0 ml of a 1M TEA in hexanessolution prior to a 1 liter isobutane charge. The reactor was thenpressurized to 550 psig with ethylene. No ethylene consumption wasdetected, therefore 30 psi of dihydrogen was charged to the reactorwhich initiated ethylene consumption.

Run 20: 0.202 g of Product V (prepared in dimethoxyethane (DME)solvent), 6.0 ml of a 1.9M TEA in toluene solution, and 2.0 g of AlPO₄(P/Al mole ratio=0.4) were mixed with 15 ml toluene at ambienttemperature. The formation of a brown solution and the completedissolution of Product V resulted immediately upon mixing. The brownsolution was stirred for 48 hours. The supported catalyst was filteredfrom the solution as a brown solid, rinsed twice with toluene, and thentwice with pentane. 0.0671 g of the catalyst was charged directly to thereactor for polymerization. 1.0 ml of a 0.5% TEA in heptanes solutionwas charged to the reactor after the catalyst charge but before theisobutane (reactor solvent) charge to purge feedstock poisons.

The data in Table XVI show that the inventive chromium compounds can beused either supported (Runs 1-16, 20) or unsupported (Runs 17-19) topolymerize and/or trimerize olefins. Furthermore, conditions can bevaried to increase the amount of trimer product (Runs 1-5 and 9) or tohave a higher yield of solid, or polymer, product (Runs 6, 7, and 13).Runs 1, 3, and 20 demonstrate that high activities are attainable.

                                      TABLE XVI                                   __________________________________________________________________________    Run.sup.a                                                                        Catalyst     Support.sup.b                                                                        Products      Activity.sup.c                           __________________________________________________________________________     1 (V)/TEA/Toluene                                                                            AlPO.sub.4                                                                           98.4% liquids, 1.6% solids                                                                  1030                                      2 (V)/TEA/Diethylbenzene                                                                     AlPO.sub.4                                                                           99.4% liquids, 0.6% solids                                                                   730                                      3 (V)/TEA/Toluene                                                                            AlPO.sub.4                                                                           99.4% liquids, 0.6% solids                                                                  1450                                      4 (I)/TEA/Toluene                                                                            AlPO.sub.4                                                                           98.6% liquids, 1.4% solids                                                                   360.sup.d                                5 (II)/TEA/Toluene                                                                           AlPO.sub.4                                                                           98.2% liquids, 1.8% solids                                                                   580                                      6 (V)/TEA/Toluene                                                                            SiO.sub.2                                                                            89.0% liquids, 11.0% solids                                                                  80                                       7 (II)/TEA/Toluene                                                                           Al.sub.2 O.sub.3                                                                     55.8% liquids, 44.2% solids                                                                  50                                       8 (I)/TEA/Toluene                                                                            SiO.sub.2                                                                            93.3% liquids, 6.7% solids                                                                   400                                      9 (III)/TEA/Toluene                                                                          AlPO.sub.4                                                                           99.8% liquids, 0.2% solids                                                                   100                                     10 (V)/TEA/Toluene                                                                            AlPO.sub.4 (.9)                                                                      96.8% liquids, 3.2% solids                                                                   930                                     11 (V)/TEA/Toluene                                                                            AlPO.sub.4                                                                           (trace) liquids, (trace) solids                                                             unreactive                               12 (V)/TEA/Toluene                                                                            P/SiO.sub.2                                                                          98.1% liquids, 1.9% solids                                                                   90                                      13 (II)/TEA/Diethylbenzene                                                                    F/Al.sub.2 O.sub.3                                                                   88.0% liquids, 12.0% solids                                                                  300                                     14 (VI)/TEA/Toluene                                                                           SiO.sub.2                                                                            94.3% liquids, 5.7% solids                                                                   40                                      15 (V)/DME      AlPO.sub.4                                                                           98.0% liquids, 2.0% solids                                                                   550                                     16 (V)/TEA/Benzene                                                                            AlPO.sub.4                                                                           99.1% liquids, 0.9% solids                                                                   500                                     17 (I)/TEA      unsupported                                                                          98.3% liquids, 1.7% solids                                                                   340                                     18 (VI)/TEA     unsupported                                                                          99.4% liquids, 0.6% solids                                                                   180                                     19 (VI)/TEA     unsupported                                                                          98.1% liquids, 1.9% solids                                                                   230                                     20 (V)/TEA      AlPO.sub.4                                                                           99.5% liquids, 0.5% solids                                                                  2760                                     __________________________________________________________________________     .sup.a All runs were made at 90° C., isobutane solvent, 550 psi        total pressure.                                                               .sup.b P/Al mole ratio = 0.4; except Run 10 whereby P/Al mole ratio = 0.9     .sup.c Grams product/grams catalyst/hour based on 30 min. run times.          .sup.d Believed to to be lower than actual due to experimental error;         actual value believe to be near 2000.                                    

                  TABLE XVII                                                      ______________________________________                                        Run  C4     1-hexene C6   C8   C10  C12  C14  C16-C28                         ______________________________________                                        1    0.05   81.92    7.76 0.49 9.12 0.09 0.52 .05                             2    0.10   78.80    7.49 0.58 11.36                                                                              0.10 1.01 .56                             3    0.06   82.19    7.68 0.45 8.85 0.08 0.58 .11                             5    0.10   83.40    7.08 0.62 8.08 0.05 0.42 .25                             6    0.55   78.70    5.52 1.84 11.24                                                                              0.42 1.26 .47                             16   0.06   72.85    13.61                                                                              0.31 12.06                                                                              0.09 0.93 .09                             19   6.03   71.66    6.09 3.61 9.42 1.17 1.41 .61                             ______________________________________                                    

EXAMPLE IX

Single crystal x-ray structures were obtained for Cr(NC₄ H₄)₃ Cl(O₂ C₂H₄ (CH₃)₂)₃ Na, shown in FIGS. 7 and 8, and Cr(NC₄ H₄)₃ Cl(O₂ C₂ H₄(CH₃)₂), and shown in FIG. 9. These crystals were obtained in accordancewith the procedure given in Example III. However, x-ray quality crystalswere obtained after the dark green, filtered solution was maintained atambient temperature and pressure under an inert atmosphere, nitrogen,for a time of about 2 days. Analysis calculated for C₂₄ H₄₂ N₃ O₆CrNaCl: C, 49-78; H, 7.31; N, 7.26% by weight. Found: C, 49.80; H 7.39;N, 7.18% by weight.

The description of the single-crystal sample and mounting used for datacollection are as follows:

Color: Green/black

Shape: Rectangular parallelepiped

Dimensions: 0.44×0.62×0.62 mm

Crystal Mount: Crystal was glued to the inside of a thin-walled glasscapillary and sealed under N₂.

Crystal Orientation: Crystal was oriented with its longer edges nearlyparallel to the phi axis of the diffractometer.

Width at Half-height from ω Scans: 0.38°

The space group and cell data are as follows:

Crystal System: Monoclinic

Space Group and Number:² P2₁ /c-C_(2h) ⁵ (No. 14)

Number of Computer-Centered Reflections Used in the Least-Squares

Refinement of the Cell Dimensions: 15 20°>25°, °C.=20±1

Lattice Constants with esd's:

    ______________________________________                                        a = 8.135(2)Å                                                                           α = 90.00°                                                                    V = 3027(1)Å.sup.3                             b = 22.337(5)Å                                                                          β = 91.67(2)°                                                                  Z = 4                                              c = 16.667(4)Å                                                                          δ = 90.00°                                                                    λ = 0.71073Å                            ______________________________________                                    

Molecular Weight: 579.05 amu

Calculated Density: 1.271 g/cn⁻³

Linear Absorption Coefficient:^(3a) 0.51 mm⁻¹

Tables XVIII-XXII list the resultant parameters used to generate themolecular structures shown in FIGS. 7 and 8.

                  TABLE XVIII                                                     ______________________________________                                        Atomic Coordinates for Nonhydrogen Atoms in                                   Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                                                      Equivalent Isotropic                                 Atom   Fractional Coordinates                                                                          Thermal Parameter,                                   Type.sup.b                                                                           10.sup.4 x                                                                             10.sup.4 y                                                                             10.sup.4 z                                                                          B, Å.sup.2 × 10.sup.c                ______________________________________                                        Cr     -1030(1) 559(1)   3005(1)                                                                             30(1)                                          Cl     135(1)   -26(1)   1981(1)                                                                             41(1)                                          Na     -2167(2) -1011(1) 1832(1)                                                                             46(1)                                          N.sub.1                                                                              -3062(4) 65(2)    2907(2)                                                                             35(1)                                          C.sub.11                                                                             -4107(5) 63(2)    2251(3)                                                                             40(1)                                          C.sub.12                                                                             -5189(5) -409(2)  2291(3)                                                                             51(1)                                          C.sub.13                                                                             -4810(5) -713(2)  2998(3)                                                                             51(1)                                          C.sub.14                                                                             -3512(5) -414(2)  3361(3)                                                                             46(1)                                          N.sub.2                                                                              -1817(4) 1027(2)  3950(2)                                                                             37(1)                                          C.sub.21                                                                             -1188(6) 1558(2)  4234(3)                                                                             47(1)                                          C.sub.22                                                                             -2205(7) 1790(2)  4799(3)                                                                             60(2)                                          C.sub.23                                                                             -3499(7) 1398(2)  4874(3)                                                                             60(2)                                          C.sub.24                                                                             -3248(5) 934(2)   4349(2)                                                                             43(1)                                          N.sub.3                                                                              -1892(4) 1185(2)  2260(2)                                                                             35(1)                                          C.sub.31                                                                             -3100(5) 1588(2)  2434(3)                                                                             41(1)                                          C.sub.32                                                                             -3573(6) 1901(2)  1757(3)                                                                             53(1)                                          C.sub.33                                                                             -2631(6) 1686(2)  1130(3)                                                                             51(1)                                          C.sub.34                                                                             -1620(6) 1249(2)  1453(3)                                                                             46(1)                                          O.sub.1a                                                                             1317(3)  971(1)   3154(2)                                                                             40(1)                                          O.sub.2a                                                                             153(3)   -12(1)   3878(2)                                                                             40(1)                                          C.sub.1a                                                                             2459(5)  631(2)   3651(3)                                                                             53(1)                                          C.sub.2a                                                                             1443(6)  329(2)   4268(3)                                                                             53(1)                                          C.sub.3a                                                                             2156(6)  1247(2)  2495(3)                                                                             58(2)                                          C.sub.4a                                                                             653(6)   -625(2)  3733(3)                                                                             49(1)                                          O.sub.1b                                                                             -2558(4) -783(2)  398(2)                                                                              62(1)                                          O.sub.2b                                                                             -3877(5) -1772(2) 1111(2)                                                                             76(1)                                          C.sub.1b                                                                             -3618(9) -1166(3) -25(4)                                                                              89(2)                                          C.sub.2b                                                                             -3627(9) -1765(3) 302(4)                                                                              83(2)                                          C.sub.3b                                                                             -2410(8) -207(3)  61(4) 79(2)                                          C.sub.4b                                                                             -4149(9) -2328(3) 1440(5)                                                                             106(3)                                         O.sub.1c                                                                             -1334(4) -1823(2) 2911(2)                                                                             65(1)                                          O.sub.2c                                                                             235(5)   -1589(2) 1529(3)                                                                             87(2)                                          C.sub.1c                                                                             71(7)    -2144(3) 2724(4)                                                                             83(2)                                          C.sub.2c                                                                             951(8)   -1913(4) 2067(4)                                                                             107(3)                                         C.sub.3c                                                                             -2090(8) -2017(3) 3614(4)                                                                             83(2)                                          C.sub.4c                                                                             1224(8)  -1393(3) 900(4)                                                                              88(2)                                          ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c This is onethird of the trace of the orthogonalized B.sub.ij           tensor.                                                                  

                  TABLE XIX                                                       ______________________________________                                        Anisotropic Thermal Parameters for Nonhydrogen Atoms                          in Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4       (CH.sub.3).sub.2).sub.3 Na].sup.a,b                                           Atom  Anisotropic Thermal Parameter (Å.sup.2 × 10)                  Type.sup.c                                                                          B.sub.11  B.sub.22                                                                              B.sub.33                                                                             B.sub.12                                                                            B.sub.13                                                                            B.sub.23                           ______________________________________                                        Cr    28(1)     31(1)   30(1)  2(1)  -0(1) -2(1)                              Cl    39(1)     43(1)   41(1)  2(1)  5(1)  -9(1)                              Na    47(1)     48(1)   44(1)  0(1)  3(1)  -4(1)                              N.sub.1                                                                             31(1)     39(2)   35(2)  0(1)  2(1)  -3(1)                              C.sub.11                                                                            31(2)     47(2)   41(2)  0(2)  -1(2) -7(2)                              C.sub.12                                                                            33(2)     59(3)   61(3)  -3(2) -4(2) -16(2)                             C.sub.13                                                                            35(2)     39(2)   79(3)  -6(2) 8(2)  3(2)                               C.sub.14                                                                            39(2)     45(2)   54(2)  1(2)  2(2)  10(2)                              N.sub.2                                                                             36(2)     38(2)   36(2)  7(1)  -3(1) -8(1)                              C.sub.21                                                                            55(2)     38(2)   47(2)  9(2)  -6(2) -5(2)                              C.sub.22                                                                            88(3)     46(3)   44(2)  32(2) -9(2) -12(2)                             C.sub.23                                                                            65(3)     74(3)   42(2)  32(2) 7(2)  0(2)                               C.sub.24                                                                            37(2)     55(2)   37(2)  14(2) -0(2) 1(2)                               N.sub.3                                                                             38(2)     35(2)   32(2)  3(1)  0(1)  -0(1)                              C.sub.31                                                                            35(2)     43(2)   43(2)  6(2)  -3(2) 1(2)                               C.sub.32                                                                            52(2)     47(2)   58(3)  8(2)  -11(2)                                                                              6(2)                               C.sub.33                                                                            62(3)     51(3)   39(2)  -2(2) -8(2) 12(2)                              C.sub.34                                                                            52(2)     45(2)   40(2)  -1(2) 2(2)  2(2)                               O.sub.1a                                                                            32(1)     40(1)   50(2)  -1(1) -3(1) -5(1)                              O.sub.2a                                                                            40(1)     38(1)   41(1)  6(1)  -7(1) -1(1)                              C.sub.1a                                                                            33(2)     50(3)   73(3)  4(2)  -13(2)                                                                              -10(2)                             C.sub.2a                                                                            53(2)     55(3)   51(2)  10(2) -24(2)                                                                              -10(2)                             C.sub.3a                                                                            45(2)     53(3)   76(3)  -15(2)                                                                              8(2)  -5(3)                              C.sub.4a                                                                            50(2)     40(2)   58(3)  12(2) -8(2) -1(2)                              O.sub.1b                                                                            76(2)     63(2)   47(2)  -14(2)                                                                              -5(2) 1(2)                               O.sub.2b                                                                            101(3)    62(2)   63(2)  -28(2)                                                                              -5(2) -2(2)                              C.sub.1b                                                                            120(5)    91(4)   56(3)  -29(4)                                                                              -25(3)                                                                              -3(3)                              C.sub.2b                                                                            116(5)    64(3)   68(4)  -18(3)                                                                              -24(3)                                                                              -12(3)                             C.sub.3b                                                                            81(4)     84(4)   72(4)  -9(3) -1(3) 19(3)                              C.sub.4b                                                                            118(5)    84(4)   113(5) -51(4)                                                                              -38(4)                                                                              29(4)                              O.sub.1c                                                                            61(2)     64(2)   70(2)  8(2)  0(2)  4(2)                               O.sub.2c                                                                            74(2)     76(3)   112(3) 29(2) 31(2) 30(2)                              C.sub.1c                                                                            73(3)     65(3)   113(5) 23(3) 9(3)  25(3)                              C.sub.2c                                                                            83(4)     143(6)  96(5)  61(4) 24(4) 14(5)                              C.sub.3c                                                                            84(4)     64(3)   101(5) -8(3) 3(4)  16(3)                              C.sub.4c                                                                            77(4)     98(5)   90(5)  13(3) 29(3) -5(4)                              ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b The form of the anisotropic thermal parameter is given in referenc     8 on page 6 of the crystal structure analysis report.                         .sup.c Atoms are labeled in agreement with FIG. 7.                       

                  TABLE XX                                                        ______________________________________                                        Atomic Coordinates for Hydrogen Atoms in Crystalline                          [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4 (CH.sub.3).sub.2)    .sub.3 Na].sup.a                                                              Atom     Fractional Coordinates                                               Type.sup.b                                                                             10.sup.4 x    10.sup.4 y                                                                            10.sup.4 z                                     ______________________________________                                        H.sub.11 -4089           350   1823                                           H.sub.12 -6043          -509   1905                                           H.sub.13 -5349         -1064   3195                                           H.sub.14 -2993          -526   3863                                           H.sub.21  -188          1740   4063                                           H.sub.22 -2044          2158   5089                                           H.sub.23 -4404          1441   5226                                           H.sub.24 -3967           597   4273                                           H.sub.31 -3554          1644   2954                                           H.sub.32 -4392          2210   1720                                           H.sub.33 -2680          1817    581                                           H.sub.34  -840          1021   1159                                           H.sub.1aa                                                                               3014           339   3336                                           H.sub.1ab                                                                               3254           892   3906                                           H.sub.2aa                                                                                967           626   4606                                           H.sub.2ab                                                                               2127           67    4588                                           H.sub.3aa                                                                               1391          1487   2185                                           H.sub.3ab                                                                               2589           938   2162                                           H.sub.3ac                                                                                3040         1495   2696                                           H.sub.4aa                                                                               -256          -834   3484                                           H.sub.4ab                                                                                926          -806   4242                                           H.sub.4ac                                                                               1586          -646   3395                                           H.sub.1ba                                                                              -4712         -1006   -11                                            H.sub.1bb                                                                              -3277         -1186   -570                                           H.sub.2ba                                                                              -2588         -1951    204                                           H.sub.2bb                                                                              -4492         -1988    37                                            H.sub.3ba                                                                              -1696           26     407                                           H.sub.3bb                                                                              -3461          -14      7                                            H.sub.3bc                                                                              -1935          -243   -458                                           H.sub.4ba                                                                              -4380         -2289   2000                                           H.sub.4bb                                                                              -3108         -2524   1385                                           H.sub.4bc                                                                              -4998         -2561   1178                                           H.sub.1ca                                                                                795         -2146   3189                                           H.sub.1cb                                                                               -255         -2547   2596                                           H.sub.2ca                                                                               1398         -2252   1795                                           H.sub.2cb                                                                               1831         -1676   2294                                           H.sub.3ca                                                                              -3168         -1848   3661                                           H.sub.3cb                                                                              -1397         -1884   4055                                           H.sub.3cc                                                                              -2164         -2446   3624                                           H.sub.4ca                                                                                456         -1357    454                                           H.sub.4cb                                                                               2033         -1690    780                                           H.sub.4cc                                                                               1756         -1015    996                                           ______________________________________                                         .sup.a The 6 methyl groups were refined as rigid rotors with                  sp.sup.3hybridized geometry and C--H bond lengths of 0.96Å. The           initial orientation of each methyl group was determined from difference       Fourier positions for the hydrogen atoms. The final orientation of each       methyl group was determined by three rotational parameters. The refined       positions for the rigid rotor methyl groups gave O--C--H angles which         ranged from 103° to 115°. The remaining hydrogen atoms were     included in the structure factor calculations as idealized atoms (assumin     sp.sup.2 or sp.sup.3hybridization of the carbon atoms and a C--H bond         length of 0.96Å) "riding" on their respective carbon atoms. The           isotropic thermal parameter of each hydrogen was fixed at 1.2 times the       equivalent isotropic thermal parameter of the carbon atom to which it is      covalently bonded.                                                            .sup.b Hydrogens are labeled with the same subscripts as their carbon         atoms with an additional literal subscript (a, b or c) where necessary to     distinguish between hydrogen atoms bonded to the same carbon.            

                  TABLE XXI                                                       ______________________________________                                        Bond Lengths Involving Nonhydrogen Atoms in                                   Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                             Type.sup.b                                                                              Length, Å                                                                             Type.sup.b Length, Å                                ______________________________________                                        Cr-Cl     2.369(1)    Cr-N.sub.1 1.990(3)                                                           Cr-N.sub.2 2.010(3)                                     Cr-O.sub.1a                                                                             2.128(3)    Cr-N.sub.3 1.986(3)                                     Cr-O.sub.2a                                                                             2.142(3)                                                            N.sub.1 -C.sub.11                                                                       1.365(5)    C.sub.11 -C.sub.12                                                                       1.376(6)                                     N.sub.1 -C.sub.14                                                                       1.366(6)    C.sub.12 -C.sub.13                                                                       1.386(7)                                     N.sub.2 -C.sub.21                                                                       1.370(6)    C.sub.13 -C.sub.14                                                                       1.376(6)                                     N.sub.2 -C.sub.24                                                                       1.374(5)    C.sub.21 -C.sub.22                                                                       1.373(7)                                     N.sub.3 -C.sub.31                                                                       1.370(5)    C.sub.22 -C.sub.23                                                                       1.377(8)                                     N.sub.3 -C.sub.34                                                                       1.376(6)    C.sub.23 -C.sub.24                                                                       1.375(7)                                                           C.sub.31 -C.sub.32                                                                       1.373(7)                                     O.sub.1a -C.sub.1a                                                                      1.443(5)    C.sub.32 -C.sub.33                                                                       1.399(7)                                     O.sub.1a -C.sub.3a                                                                      1.448(6)    C.sub.33 -C.sub.34                                                                       1.375(7)                                     O.sub.2a -C.sub.2a                                                                      1.437(5)                                                            O.sub.2a -C.sub.4a                                                                      1.450(5)    C.sub.1a -C.sub.2a                                                                       1.498(7)                                     O.sub.1b -C.sub.1b                                                                      1.391(8)    C.sub.1b -C.sub.2b                                                                       1.445(9)                                     O.sub.1b -C.sub.3b                                                                      1.410(7)    C.sub.1c -C.sub.2c                                                                       1.422(10)                                    O.sub.2b -C.sub.2b                                                                      1.370(7)                                                            O.sub. 2b -C.sub.4b                                                                     1.379(8)    Na . . . Cr                                                                              4.108(2)                                     O.sub.1c -C.sub.1c                                                                      1.392(7)                                                            O.sub.1c -C.sub.3c                                                                      1.408(8)    Na-Cl      2.896(2)                                     O.sub.2c -C.sub.2c                                                                      1.278(9)                                                            O.sub.2c -C.sub.4c                                                                      1.409(8)    Na-N.sub.1 3.098(4)                                     Na-C.sub.11                                                                             2.967(5)    Na-O.sub.1b                                                                              2.454(4)                                     Na-C.sub.12                                                                             2.924(5)    Na-O.sub.2b                                                                              2.483(4)                                     Na-C.sub.13                                                                             3.015(5)    Na-O.sub.1c                                                                              2.629(5)                                     Na-C.sub.14                                                                             3.104(5)    Na-O.sub.2c                                                                              2.408(5)                                     Na-C.sub.g1.sup.c                                                                       2.788(--)                                                           ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the fivemembered ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13,       and C.sub.14 ; this value is therefore listed without an estimated            standard deviation.                                                      

                  TABLE XXII                                                      ______________________________________                                        Bond Angles Involving Nonhydrogen Atoms in                                    Crystalline [Cr(NC.sub.4 H.sub.4).sub.3 (Cl)(O.sub.2 C.sub.2 H.sub.4          (CH.sub.3).sub.2).sub.3 Na].sup.a                                             Type.sup.b Angle, deg.                                                                              Type.sup.b Angle, deg.                                  ______________________________________                                        ClCrN.sub.1                                                                               89.1(1)   ClCrN.sub.2                                                                              173.9(1)                                     N.sub.1 CrN.sub.2                                                                         94.0(1)   ClCrN.sub.3                                                                               94.5(1)                                     N.sub.1 CrN.sub.3                                                                         93.5(1)   N.sub.2 CrN.sub.3                                                                         90.5(1)                                     ClCrO.sub.1a                                                                              86.9(1)   N.sub.1 CrO.sub.1a                                                                       171.9(1)                                     N.sub.2 CrO.sub.1a                                                                        89.4(1)   N.sub.3 CrO.sub.1a                                                                        93.8(1)                                     ClCrO.sub.2a                                                                              88.9(1)   N.sub.1 CrO.sub.2a                                                                        94.7(1)                                     N.sub.2 CrO.sub.2a                                                                        85.7(1)   N.sub.3 CrO.sub.2a                                                                       171.2(1)                                     O.sub.1a CrO.sub.2a                                                                       78.2(1)                                                           CrN.sub.1 C.sub.11                                                                       124.4(3)   C.sub.11 N.sub.1 C.sub.14                                                                105.7(3)                                     CrN.sub.1 C.sub.14                                                                       128.6(3)   C.sub.21 N.sub.2 C.sub.24                                                                106.1(4)                                     CrN.sub.2 C.sub.21                                                                       126.6(3)   C.sub.31 N.sub.3 C.sub.34                                                                106.0(3)                                     CrN.sub.2 C.sub.24                                                                       126.5(3)                                                           CrN.sub.3 C.sub.31                                                                       125.0(3)   CrO.sub.1a C.sub.1a                                                                      113.5(2)                                     CrN.sub.3 C.sub.34                                                                       128.3(3)   CrO.sub.1a C.sub.3a                                                                      122.5(3)                                                           C.sub.1a O.sub.1a C.sub.3a                                                               110.5(3)                                     N.sub.1 C.sub.11 C.sub.12                                                                110.3(4)   CrO.sub.2a C.sub.2a                                                                      107.4(2)                                     C.sub.11 C.sub.12 C.sub.13                                                               106.9(4)   CrO.sub.2a C.sub.4a                                                                      124.9(3)                                     C.sub.12 C.sub.13 C.sub.14                                                               106.5(4)   C.sub.2a O.sub.2a C.sub.4a                                                               111.8(3)                                     N.sub.1 C.sub.14 C.sub.13                                                                110.6(4)   C.sub.1b O.sub.1b C.sub.3b                                                               114.7(4)                                     N.sub.2 C.sub.21 C.sub.22                                                                109.7(4)   C.sub.2b O.sub.2b C.sub.4b                                                               115.6(5)                                     C.sub.21 C.sub.22 C.sub.23                                                               107.4(4)   C.sub.1c O.sub.1c C.sub.3c                                                               114.2(5)                                     C.sub.22 C.sub.23 C.sub.24                                                               107.1(4)   C.sub.2c O.sub.2c C.sub.4c                                                               116.0(5)                                     N.sub.2 C.sub.24 C.sub.23                                                                109.7(4)                                                           N.sub.3 C.sub.31 C.sub.32                                                                110.3(4)   O.sub.1a C.sub.1a C.sub.2a                                                               105.8(3)                                     C.sub.31 C.sub.32 C.sub.33                                                               107.0(4)   O.sub.2a C.sub.2a C.sub.1a                                                               109.8(4)                                     C.sub.32 C.sub.33 C.sub.34                                                               106.6(4)   O.sub.1b C.sub.1b C.sub.2b                                                               112.8(5)                                     N.sub.3 C.sub.34 C.sub.33                                                                110.2(4)   O.sub.2b C.sub.2b C.sub.1b                                                               112.6(5)                                                           O.sub.1c C.sub.1c C.sub.2c                                                               114.9(6)                                     ClNaC.sub.g1.sup.c                                                                        83.6(--)  O.sub.2c C.sub.2c C.sub.1c                                                               121.1(6)                                     ClNaO.sub.1b                                                                              89.5(1)   C.sub.g1 NaO.sub.1b.sup.c                                                                111.1(--)                                    ClNaO.sub.2b                                                                             156.0(1)   C.sub.g1 NaO.sub.2b.sup.c                                                                110.2(--)                                    ClNaO.sub.1c                                                                             108.2(1)   C.sub.g1 NaO.sub.1c.sup.c                                                                 99.4(--)                                    ClNaO.sub.2c                                                                              84.2(1)   C.sub.g1 NaO.sub.2c.sup.c                                                                155.9(--)                                    ClNaN.sub.1                                                                               61.5(1)   O.sub.1b NaO.sub.2b                                                                       67.4(2)                                     ClNaC.sub.11                                                                              73.3(2)   O.sub.1b NaO.sub.1c                                                                      146.4(2)                                     ClNaC.sub.12                                                                             100.0(2)   O.sub.1b NaO.sub.2c                                                                       89.4(2)                                     ClNaC.sub.13                                                                             104.4(2)   O.sub.2b NaO.sub.1c                                                                       89.3(2)                                     ClNaC.sub.14                                                                              81.1(2)   O.sub.2b NaO.sub.2c                                                                       88.8(2)                                                           O.sub.1c NaO.sub.2c                                                                       65.1(2)                                     N.sub.1 NaC.sub.11                                                                        25.9(2)                                                           N.sub.1 NaC.sub.14                                                                        25.5(2)   N.sub.1 NaC.sub.12                                                                        43.8(2)                                     C.sub.11 NaC.sub.12                                                                       27.0(2)   N.sub.1 NaC.sub.13                                                                        43.2(2)                                     C.sub.12 NaC.sub.13                                                                       26.9(2)   C.sub.11 NaC.sub.13                                                                       43.5(2)                                     C.sub.13 NaC.sub.14                                                                       25.9(2)   C.sub.12 NaC.sub.14                                                                       42.9(2)                                                           C.sub.11 NaC.sub.14                                                                       41.9(2)                                     ______________________________________                                         .sup.a The numbers in parentheses are the estimated standard deviations i     the last significant digit.                                                   .sup.b Atoms are labeled in agreement with FIG. 7.                            .sup.c The symbol C.sub.g1 is used to designate the center of gravity for     the fivemembered ring containing N.sub.1, C.sub.11, C.sub.12, C.sub.13,       and C.sub.14 ; this value is therefore listed without an estimated            standard deviation.                                                      

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A polymerization process comprisingcontacting at least one mono-1-olefin with an alkyl aluminum activatingcompound and a catalyst prepared by a process comprising forming amixture of and refluxing:(a) a chromium salt; (b) a metal amide, whichis a pyrrolide; and (c) an electron pair donor solvent which can affecta reaction between the chromium salt and metal amide.
 2. A process topolymerize olefins comprising contacting at least one mono-1-olefin witha composition comprising of Cr₅ (C₄ H₄ N)₁₀ (C₄ H₈ O)₄ supported on aninorganic oxide and an alkyl aluminum activating compound.
 3. A processto polymerize olefins comprising contacting at least one mono-1-olefinwith a composition comprising Cr(C₄ H₄ N)₄ Na₂.2(OC₄ H₈) supported on aninorganic oxide and an alkyl aluminum activating compound.
 4. A processto polymerize olefins comprising contacting at least one mono-1-olefinwith a composition comprising Cr(C₄ H₄ N)₅ (OC₄ H₈)Na₂. 4(OC₄ H₈)supported on an inorganic oxide and an alkyl aluminum activatingcompound.
 5. A process to polymerize olefins comprising contacting atleast one mono-1-olefin with a catalyst system prepared according to aprocess comprising:(a) forming a mixture of and refluxing a chromiumsalt, a metal amide which is a pyrrolide, and electron pair donorsolvent which can affect a reaction between the chromium salt and metalamide; (b) recovering a chromium-containing compound from the mixture of(a); (c) reacting the chromium-containing compound of (b) with anaromatic compound and an alkyl aluminum activating compound to form areaction product; (d) adding an inorganic oxide to the reaction productof (c); and (e) recovering a solid product.
 6. A process to polymerizeolefins comprising contacting at least one mono-1-olefin with a catalystsystem prepared according to a process comprising:(a) forming a mixtureof and refluxing a chromium salt, a metal amide which is a pyrrolide,and an electron pair donating solvent which can affect a reactionbetween the chromium salt and metal amide; (b) adding an inorganic oxideto the mixture of (a) to form a slurry; (c) recovering a supportedchromium-containing solid product; (d) adding an alkyl aluminumactivating compound to the solid product of (c); and (e) recovering asolid product.
 7. A process to polymerize olefins comprising contactingat least one mono-1-olefin with a catalyst composition comprising Cr(NC₄H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na supported on an inorganic oxide and analkyl aluminum activating compound.
 8. A process to polymerize olefinscomprising contacting at least one mono-1-olefin with a catalyst systemprepared according to the process comprising:(a) forming a mixture ofand refluxing a chromium salt, a metal amide which is a pyrrolide, andelectron pair donor solvent which can affect a reaction between thechromium salt and metal amide; (b) recovering a chromium-containingcompound from the mixture of (a); and (c) reacting thechromium-containing compound of (b) with an alkyl aluminum activatingcompound to form a reaction product.
 9. A process according to claim 1wherein said mono-1-olefin has from 2 to about 8 carbon atoms permolecule and said contacting occurs under slurry polymerizationconditions.
 10. A process according to claim 2 wherein saidmono-1-olefin has from 2 to about 8 carbon atoms per molecule and saidcontacting occurs under slurry polymerization conditions.
 11. A processaccording to claim 3 wherein said mono-1-olefin has from 2 to about 8carbon atoms per molecule and said contacting occurs under slurrypolymerization conditions.
 12. A process according to claim 4 whereinsaid mono-1-olefin has from 2 to about 8 carbon atoms per molecule andsaid contacting occurs under slurry polymerization conditions.
 13. Aprocess according to claim 5 wherein said mono-1-olefin has from 2 toabout 8 carbon atoms per molecule and said contacting occurs underslurry polymerization conditions.
 14. A process according to claim 6wherein said mono-1-olefin has from 2 to about 8 carbon atoms permolecule and said contacting occurs under slurry polymerizationconditions.
 15. A process according to claim 7 wherein saidmono-1-olefin has from 2 to about 8 carbon atoms per molecule and saidcontacting occurs under slurry polymerization conditions.
 16. A processaccording to claim 8 wherein said mono-1-olefin has from 2 to about 8carbon atoms per molecule and said contacting occurs under slurrypolymerization conditions.
 17. A process according to claim 1 whereinsaid activating compound and said catalyst are supported on an inorganicoxide support.
 18. A process according to claim 17 wherein saidactivating compound, said catalyst and said inorganic oxide support arecombined in the presence of an aromatic hydrocarbon having from about 6to about 50 carbon atoms per molecule.
 19. A process according to claim2 wherein said activating compound, Cr₅ (C₄ H₄ N)₁₀ (C₄ H₈ O)₄ and saidinorganic oxide support are combined in the presence of an aromatichydrocarbon having from about 6 to about 50 carbon atoms per molecule.20. A process according to claim 3 wherein said activating compound,Cr(C₄ H₄ N)₄ Na₂.2(OC₄ H₈) and said inorganic oxide support are combinedin the presence of an aromatic hydrocarbon having from about 6 to about50 carbon atoms per molecule.
 21. A process according to claim 4 whereinsaid activating compound, Cr(C₄ H₀ N)₅ (OC₄ H₈)Na₂.4(OC₄ H₈) and saidinorganic oxide support are combined in the presence of an aromatichydrocarbon having from about 6 to about 50 carbon atoms per molecule.22. A process according to claim 5 wherein said activating compound,said chromium-containing compound and said inorganic oxide support arecombined in the presence of an aromatic hydrocarbon having from about 6to about 50 carbon atoms per molecule.
 23. A process according to claim6 wherein said activating compound and said supportedchromium-containing solid product are combined in the presence of anaromatic hydrocarbon having from about 6 to about 50 carbon atoms permolecule.
 24. A process according to claim 7 wherein said activatingcompound, Cr(NC₀ H₄)₃ Cl(O₂ C₂ H₄ (CH₃)₂)₃ Na and said inorganic oxidesupport are combined in the presence of an aromatic hydrocarbon havingfrom about 6 to about 50 carbon atoms per molecule.
 25. A processaccording to claim 8 wherein said activating compound, saidchromium-containing compound and said inorganic oxide support arecombined in the presence of an aromatic hydrocarbon having from about 6to about 50 carbon atoms per molecule.
 26. A process according to claim1 wherein said activating compound is a trialkylaluminum compound.
 27. Aprocess according to claim 26 wherein said trialkyaluminum compound istriethylaluminum.